JPS583217B2 - Kanko Buzai - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for manufacturing a pattern member that improves the mechanical strength of a pattern member formed on a photosensitive member whose photosensitive layer is a stack of a chalcogenide layer and a diffusive metal layer.

Conventionally, photosensitive members have been used in which a diffusive metal layer is laminated on a chalcogenide layer.

The photosensitive property of this photosensitive member is the diffusion of light into the metal chalcogenide layer.

The diffused metal acts to make the chalcogenide layer insoluble in alkali.

This makes the difference in alkali solubility between the unexposed part and the exposed part of the chalcogenide layer noticeable, giving high resolution to pattern formation by alkali etching.

The diffusion of the metal into the chalcogenide is accompanied by the relative diffusion of the chalcogenide into the metal, and phenomenonally, mutual diffusion occurs between the diffusive metal layer and the chalcogenide layer, and a diffusion layer of a different substance is formed in the exposed area. It is recognized that it is formed.

This diffusion layer is a mixed layer of metal and chalcogenide.

Moreover, the diffusion effect of metals, on the other hand, diversifies the uses of photosensitive members.

This is because the electrical properties of the diffusion layer are significantly different from those of the chalcogenide layer in terms of various properties such as electrical resistance, photoconductivity, photovoltaic property, and electrical resistance voltage dependence (so-called switching phenomenon or memory phenomenon). As well as being different from
This is because, as mentioned above, changes in chemical properties such as acid resistance and alkali elution, and physical properties such as optical density and crystallinity, are also vastly different.

These differences in characteristics are utilized as various pattern members to be described later.

For example, the optical density of the diffusion layer for visible light is between that of metals and chalcogenide, which is used for microphotography, photomasks, etc., and its electrical resistance value is between that of metals and chalcogenides. It is used as an electric circuit member by taking advantage of certain characteristics, and as a hologram by taking advantage of the difference in optical refractive index, optical transmittance, and optical density from metals and chalcogenides.

A considerable amount of exposure or irradiation time is required to irradiate light onto a photosensitive member whose basic structure is such a chalcogenide layer and a diffusive metal layer to diffuse the metal.

Such photosensitive members usually have a structure in which a chalcogenide layer and a diffusive metal layer are laminated on a substrate.

Various pattern members formed from photosensitive materials are used for industrial purposes, such as when used as a photomask and used repeatedly, and when used for a long time as a circuit member or a printing member. Good mechanical strength is required.

The pattern member is usually in the form of a high resolution pattern, the material forming the pattern being a very thin diffusion layer.

Therefore, damage to the pattern member is likely to occur.

A first object of the present invention is to provide a photosensitive member for forming a pattern member with improved mechanical strength.

Another object of the present invention is to provide a photosensitive member for reliably forming a pattern member having a negative pattern relationship with an original pattern.

The present invention provides a photosensitive member having a basic structure of a laminated layer of a chalcogenide layer and a diffusible metal layer having a metal that diffuses into the chalcogenide layer when receiving radiant energy in a structure in contact with the chalcogenide layer. , a method of manufacturing a pattern member using a photosensitive member characterized in that a photoresist layer is provided.

One of the features of the pattern member formed using the photosensitive member according to the present invention is that the pattern surface is a photoresist layer, and the pattern member is protected by the photoresist layer.

Another feature is that the photoresist layer is configured according to the shape of the pattern of the pattern member, and this configuration is, in principle, formed at the same time as the formation of the diffusion layer during pattern exposure. be.

The photoresist layer also acts as an etching mask for the etching process for forming the negative pattern.

Next, the present invention having such features will be explained in detail with reference to the drawings.

The most general construction of a photosensitive member according to the present invention is shown in FIGS. 1-4.

That is, it is composed of a diffusible metal layer 1, a chalcogenide layer 2, a substrate 3, and a photoresist layer 4.

The chalcogenide referred to in the present invention is an alloyed substance consisting of or having as a main component at least one of chalcogen elements, sulfur (S), selenium (Se), and tellurium (Te).

Typical examples that are effective in the present invention are Se, S, As-S systems,
As-Se series, As-Te series, S-Se series, Sb-Se
system, Sb-Te system, Bi-S system, Bi-Se system, Bi-
Binary chalcogenide such as Te type or As-S-Te
These are ternary chalcogenides such as As-Se-Te system and As-Se-Te system.

When forming a chalcogenide layer, it is also effective to add a small amount of elements such as halogen, Ge, Si, Tl, etc., if necessary.

Particularly in the present invention, adding a small amount of metal as an additive is effective in terms of photosensitivity.

Typical metals to be added are Ag, Cu, and Z.
n, Cd, Mn, Ga, In, Bi, Sb, Te, Se
Alternatively, alloys thereof may be mentioned, with Ag and Cu being particularly suitable.

The amount of metal added is 100 atoms, which constitute chalcogenide.
1 to 0.0 0 01 atoms, especially 9.5 to 0
．． 005 is preferred.

The thickness of the chalcogenide layer is set appropriately depending on the application, but it can be used with photomasks, various high-density circuit components that take advantage of the difference in electrical properties between the image area and the non-image area of the formed pattern, and the difference in optical density. In order to obtain high-resolution patterns such as those used in microphotographs, the chalcogenide layer is normally set to be thin, about 1000 mμ to 10 mμ.

In particular, in order to obtain a resolution of 2 μ or more, the distance is approximately 500 m.
It is set to μ~50mμ.

The lower limit of the layer thickness range is defined by manufacturing limitations for forming a uniform layer.

When a molten chalcogenide is applied, the thickness ranges from several μ to several 1
A thickness of 00μ is easy to obtain, and when cut out as a wafer, the thickness will be 10μ or more.

In normal cases, to obtain fine patterns,
The chalcogenide layer has a thickness of 700 mμ to 20 mμ, especially 1
It is set to 00 mμ to 20 mμ.

This numerical range takes into consideration the ease of forming a chalcogenide layer with a uniform composition.

If the strength is sufficient, the substrate may be omitted.

A diffusible metal layer is defined as a layer that provides metal that can be diffused into the chalcogenide layer by light.

The metals that can be diffused include all metals, and representative metals from the viewpoint of practicality include alkali metals such as Li, Na, K, Rb, and Cs, and alkali metals such as Be, Mg, Ca, Sr, and Ba. , Ag, Zn, Cd, Mn, Ga,
These are metals such as Ni, Cr, Cu, In, Sn, and T1, and compounds that dissociate and generate these metals or metal ions.

Suitable examples of these compounds include metal sulfides,
These include selenides, tellurides, oxides, and halides.

As specific examples of these, particularly preferred compounds are Cu2S
,Ag2S,Ag2Se,Ag2Te,ZnO,SrF
2, CaF2, KCI, LiBr, LiCl, LiF,
LiI, NaCl, AgI, AgBr, AgNO3, P
bI2, KAg4I5, RbAg4I5, NH4Ag4
I5, CdS, ZnS, ZnSe, etc.

As the diffusible metal layer, Ag or Cu, Ag and Cu, or an alloy containing Ag and/or Cu gives particularly effective results.

Examples of alloys include:

Cu40Ag60, Cu10Ag90, Cu20Ags
o, Cu3oAg70, Cu50Ag50, Cu66A
g40, Cu70Ag3o, CuaoAg20, Cuo
oAgto,Ag37Ga63,Ag5Hg95,Ag
30In70,Ag91Li9,Ag7Pb93,Ag
24.4Te75.6, Ag1.5Tl98.5, Cu
13Ga87, Cu2Hg98, Cu5In95, Cu
7sn93, Cu16Tre84, Ge5Sng5, M
g2.2Pb97.8, etc.

The thickness of the diffusive metal layer must be selected appropriately in relation to the intensity of the irradiated light, but it generally needs to be extremely thin, with a thickness of 50
In the case of a thickness of 0 mμ or more, it is impractical to completely interdiffuse and cause the entire diffusive metal layer to disappear due to the diffusion effect, that is, to change it into a different substance, as it requires long-term irradiation with strong light. Requires means.

Furthermore, if the thickness is extremely thin, such as 10 mμ or less, the uniformity of the diffusive metal film will be slightly disturbed, which is not preferable.

The range of 15 to 100 mμ is suitable in all respects, and for this purpose, an exposure time of several minutes using a normal strong light source such as an ultra-high pressure mercury lamp is sufficient, and for sensitive photosensitive materials, the exposure time is sufficient. The time is reduced to within a few tens of seconds.

Furthermore, if it is not expected that the diffusible metal layer will completely disappear, the diffusible metal layer may have a thickness of 500 mμ or more.

As the substrate, glass plates, metal plates, paper sheets, resin plates, ceramics, etc. are selected and used depending on the purpose.

A photoresist layer is described as a photosensitive resin layer that hardens by photopolymerization or photocrosslinking to the radiation used for pattern exposure and becomes insolubilized in specified solvents.

As the material constituting the photoresist layer, a photoresist material that has been widely used in the field of photo processing is used.

The following table lists the most typical photoresist materials.

In the table, the solvent column is an example of a solvent used for dissolving and removing the area that was not exposed to radiation (unexposed area).

For the formation of the photoresist layer, it is sufficient to use the commercially available photoresists shown in the table above, but photoresist materials may be prepared if necessary.

In this case, a photoresist layer may be formed using a photopolymerizable compound as a main component.

Typical photopolymerizable compounds are listed below.

Methoxypolyethylene glycol methacrylate, methoxypolyethylene glycol allyl methacrylate, ethylene glycol dimethacrylate, diethylene glycol dimecacrylate, triethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, 1,3-butylene glycol dimethacrylate methacrylate,
Propylene glycol dimethacrylate, polypropylene glycol dimethacrylate, trimethylolethane trimethacrylate, trimethylolpropane trimethacrylate, mixture of trimethylolbutane trimethacrylate (85%) and trimethylolpropane dimethacrylate (15%), Tetramethylolmethanetetramethacrylate, 2.
3-dibromopropyl acrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, polyethylene glycol diacrylate, trimethylolpropane triacrylate, tetramethylolmethane triacrylate, tetramethylolmethane tetraacrylate, tetramethylolmethane methacrylate, Tetramethylolmethane thiacrylate etc.

In addition to the photopolymerizable compound, penzoin alkyl ether and polyalkyl acrylate are added as necessary.

The thickness of the photoresist layer can be set relatively arbitrarily, but
The thickness is usually set to 1μ to 20μ.

A diffusive metal layer and a chalcogenide layer normally constitute a photosensitive member in the form of a two-layer stack as shown in FIGS. Three or more metal layers and chalcogenide layers may be laminated.

An example of this is shown in FIGS. 3 and 4.

Formation of a pattern member using the photosensitive member according to the present invention is carried out by performing pattern exposure and then dissolving and removing the photoresist layer in the unexposed area and at least one of the diffusive metal layer and the chalcogenide layer in the unexposed area. It is formed.

The entire surface of the pattern member thus formed is irradiated with light for the purpose of improving the mechanical strength of the photoresist layer remaining in the exposed areas.

Typical embodiments of pattern member formation are shown in FIGS. 5-10.

That is, the photosensitive member shown in FIG. 1 is subjected to pattern exposure.

Pattern exposure is performed by exposing 8 through an original pattern 5 having dark areas 6 and bright areas 7.

Due to the pattern exposure, a diffusion layer a is formed in the exposed portion 7' of the photosensitive member without any change in the unexposed portion 6'.

Simultaneously with the formation of the diffusion layer, the photoresist layer in the exposed area is photocured and converted into a solvent-resistant layer 10.

Pattern exposure and full-surface light irradiation, which will be described later, are performed using radiant energy from ultraviolet rays, visible light, near-infrared rays, and particle beams such as electron beams and ion beams.

In the case of full-surface light irradiation to improve the mechanical strength of the photoresist layer, ultraviolet light is preferred.

This type of radiation is applied with strong radiant energy.

After pattern exposure, the unexposed portions of the photoresist layer are dissolved and removed.

As a result, the shape shown in FIG. 6 is obtained.

Next, during a fixing process, the unexposed portion of the diffusive metal layer is dissolved and removed to provide a pattern member having the shape shown in FIG.

To remove the diffusible metal layer, hydrofluoric acid, nitric acid, hydrochloric acid,
Sulfuric acid and mixtures thereof, such as a mixture of hydrofluoric acid and nitric acid,
Acids such as aqua regia and a mixture of dichromic acid and sulfuric acid are used.

Especially for Ag, chromic acid monosulfuric acid mixture (K2Cr2
O7-H2S04) Copper sulfate-sulfuric acid solution (CuSO4-H
2SO4), ferric nitrate solution, red blood salt-brompotash solution (sequentially applying sodium thiosulfate solution), and for Cu, ferric chloride solution are preferred.

Furthermore, when the diffusion metal layer is made of Al, Zn, etc., an alkali may be used.

The diffusion layer is insoluble or poorly soluble in acids and alkalis.

The unexposed chalcogenide layer of the pattern member shown in FIG. 7 is dissolved and removed to provide the pattern member shown in FIG. 8.

An alkali is usually used to remove the unexposed chalcogenide layer.

Typical compositions of the alkaline solution include water or alcohol solutions of alkali hydroxides such as Li, Na, and K, or organic alkalis such as piperidine, etc., and all other alkalis are also applicable.

In particular, dilute alkali, NH4OH aqueous solution, ammonium sulfide aqueous solution, ammonium polysulfide aqueous solution, and sodium sulfide solution are preferably used.

The pattern member shown in FIG. 8 may be further subjected to other treatments depending on the use of the pattern member.

For example, etching of the substrate exposed in the unexposed portion may be performed as necessary.

The formed pattern member is irradiated with light from above the photoresist layer or from the substrate side as shown in FIG. 9, in order to further harden the photoresist layer 10 covering the exposed area.

In this manner, by finally irradiating the entire surface with light, a pattern member with high surface hardness and no change in hardness and contrast over time can be obtained.

During the removal process of the diffusive metal layer and chalcogenide layer in the unexposed areas after pattern exposure, the photoresist layer in the exposed areas acts as an etching mask to protect the exposed areas.

The diffusion layer may not be formed over the entire layer of the diffusive metal layer and chalcogenide layer depending on the exposure amount of pattern exposure.

In this case, the diffusive metal layer and chalcogenide layer that did not contribute to the diffusion remain in the exposed area, and therefore, the exposed area remains free of the photoresist layer, the diffusion layer, the residual diffusible metal layer, and/or the residual chalcogenide layer. Consists of layers.

The steps for forming the pattern member shown in FIGS. 5 to 9 are for the case where the photosensitive member shown in FIG. 1 is used, but when the photosensitive member shown in FIG. A pattern member is formed in the same manner as shown in FIGS. 5-5, except that the order of dissolving and removing the diffusible metal layer and the chalcogenide layer is changed.
In FIG. 9, a pattern member is provided in which the positions of the diffusible metal layer and the chalcogenide layer are reversed.

When the photosensitive members shown in FIGS. 3 and 4 are used, they can be similarly used to form a double-turn member, except that the process of dissolving the unexposed areas is increased.

Next, the present invention will be explained with reference to Examples.

Example 1. 15 g of arsenic, 7 g of sulfur, 36.3 g of selenium, and 8.7 g of germanium are weighed and vacuum sealed in a quartz tube.

This is heated to 980° C. in an electric furnace and heated for about 7 hours.

Thereafter, it was cooled to 750° C. over about 2 hours, then taken out from the furnace and quenched in cold water to obtain chalcogenide.

This As-S-Se-Ge chalcogenide was
It was weighed and deposited at a temperature of about 450° C. in a vacuum of 2×10 −5 Torr.

The glass substrate is kept at about 120°C.

The thickness of the deposited film was approximately 500 mμ. The color of the obtained vapor deposited film was dark reddish brown.

A thin metal layer was then deposited under the following deposition conditions.

Vacuum degree 2 x 10-6 Torr, evaporation boat temperature approximately 850
℃, and the substrate temperature was room temperature.

The deposited metal was silver, and the deposited film thickness was 25 mμ.

Furthermore, the laminated photosensitive material was placed in a rotary coater and coated with commercially available KP.
R photoresist was applied to a thickness of about 5 μm (dry thickness) to form a three-layer laminated photosensitive material.

Next, pattern exposure was performed.

For pattern exposure, a 250 W ultra-high pressure mercury lamp was used, and exposure for about 2 minutes was given from a distance of about 30 cm from the light source.

Since a photocured film of the photoresist that had been exposed to pattern light was formed here, development treatment was subsequently performed using a developer containing trichlene or a mixture of trichlene and cellosolve in appropriate amounts.

Development was completed within 1 minute.

Next, the Ag layer remaining in the unexposed area was dissolved and removed using dilute nitric acid (approximately 10 parts).

Elutes in about 5 seconds. Furthermore, chalcogenide was dissolved and removed.

The etching solution is 0. It was possible to completely dissolve it in about 30 seconds using 3N-NaOH aqueous solution.

As a result of the process described above, a pattern consisting of a chalcogen glass part in which metal is diffused and a photocured photoresist film on top of the chalcogen glass part could be formed in the exposed part.

The surface hardness of this pattern member is 380 to 400 kg/m
It was m2.

Next, from the glass substrate side, the entire surface was exposed for 1 minute from a distance of about 30 cm using a 250 W ultra-high pressure mercury lamp.

The surface hardness of the pattern member thus obtained is 420~
It was extremely excellent at 460 kg/mm2.

Example 2. A three-layer laminated sensitive material was formed using As2S3 in exactly the same manner as in Example 1.

When the thickness of the deposited As2S3 film was 500 mμ and the thickness of the deposited Ag film was 20 mμ, a pattern member with high photocuring was formed by applying pattern exposure for about 4 minutes.

The surface hardness was 180 kg/mm2 compared to 140 kg/mm2 when formed using a photosensitive member without photoresist.
It was ~200 kg/mm2.

Further, the entire surface was exposed to light for 2 minutes from the glass substrate side.

As a result, the surface hardness was 200 to 250 kg/
improved to mm2.

Example 3. In Example 1, As2S3 was used as chalcogenide.
Deposit Te0.3 to about 700 mμ, and deposit Ag to about 30 mμ.
The surface hardness of the pattern member obtained using the photosensitive member prepared by vapor deposition is 130 kg/mm2 compared to 100 kg/mm2 when no photoresist is provided.
Met.

Further, when the entire surface was exposed from the glass substrate side for 1 minute, the surface hardness was improved to about 1.50 kg/mm2.

Example 4. After thoroughly polishing the surface of the glass substrate, an Ag metal layer was first deposited.

The Ag deposition conditions were the same as in Example 1.

The thickness of the deposited film was 30 mμ.

Next, a chalcogenide layer having a composition of AS10S80Se10 was laminated by vapor deposition.

The deposited film thickness was 600 mμ.

The obtained deposited film was brown and colored.

Furthermore, a commercially available photoresist such as Fuji Resist No. 7 (trade name, manufactured by Fuji Pharmaceutical Industries, Ltd.) was applied to the laminated photosensitive material to a thickness of about 3 μm to form a three-layer laminated photoresist.

Next, pattern exposure was performed.

An exposure time of 1 minute was sufficient.

After pattern exposure, uncured portions of the photoresist were eluted and removed.

That is, it was immersed in an aqueous solution at a constant temperature for about 3 minutes.

Furthermore, the unexposed chalcogenide layer and Ag layer were dissolved and removed.

That is, using a 0.3N-NaOH aqueous solution, the former was eluted and removed by dipping for about 10 seconds, and using a 1N-ferric nitrate aqueous solution, the latter was dissolved and removed by dipping for about 5 seconds.

Therefore, a relief pattern of brown and large color contrast was formed.

The surface hardness is 200 without photoresist.
kg/mm2 versus 300 kg/mm2.

Furthermore, as a result of applying a 1-minute full-surface exposure from the photoresist side, the surface hardness was improved to 350 kg/mm2.

Example 5. An example is shown in which an acrylic curing agent is applied on the three-layer laminate of glass substrate-Ag-chalcogenide layer shown in Example 4.

The applied resist was as shown below, and the coating film thickness was about 10 μm.

A resist was prepared by mixing the above A and B agents at a weight ratio of 3:2 and was formed by coating.

Two minutes of pattern exposure was sufficient.

After exposure, the unexposed portion was dissolved and removed by immersing it in methyl ethyl ketone for about 1 minute.

Subsequently, the chalcogenide layer and the Ag layer were dissolved and removed in the same manner as in Example 4.

The surface hardness of the relief pattern was 350 kg/mm2.

Furthermore, when the entire surface was exposed for 1 minute from the photoresist side, the surface hardness of the finally obtained relief pattern further increased to reach 390 kg/ms2.

On the other hand, the resolution was approximately 1500 lines/mm.

[Brief explanation of drawings]

FIGS. 1 to 4 are schematic cross-sectional views showing one embodiment of a photosensitive member applied to the present invention. 5 to 9 are process diagrams for forming a pattern member, with FIG. 5 showing the pattern exposure step, FIGS. 6 to 8 showing the etching step, and FIG. 9 showing the entire surface light irradiation step. In the drawings, 1 is a diffusive metal layer, 2 is a chalcogenide layer, 3 is a substrate, 4 is a photoresist layer, 5 is an original pattern, 6 is a dark area, 7 is a bright area 9 is a diffusion layer, 10 is a photocured photoresist layer and 1
1 indicates full-surface light irradiation.

Claims (1)

[Claims] 1. A photoresist layer is deposited on a photosensitive layer having a basic structure consisting of a lamination of a chalcogenide layer and a diffusible metal layer having a metal that diffuses into the chalcogenide layer when receiving radiant energy in a structure in contact with the chalcogenide layer.
After pattern exposure is applied to a photosensitive member provided to a thickness of μ to 20 μ, the unexposed portions of the photoresist layer, diffusive metal layer, and chalcogenide layer are removed, and then the remaining photoresist layer is irradiated with light over the entire surface. A method for manufacturing a pattern member, characterized in that: