KR20090015015A - Substrate for photomask, photomask and method for manufacturing thereof - Google Patents
Substrate for photomask, photomask and method for manufacturing thereof Download PDFInfo
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- KR20090015015A KR20090015015A KR1020087012290A KR20087012290A KR20090015015A KR 20090015015 A KR20090015015 A KR 20090015015A KR 1020087012290 A KR1020087012290 A KR 1020087012290A KR 20087012290 A KR20087012290 A KR 20087012290A KR 20090015015 A KR20090015015 A KR 20090015015A
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- layer
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- photomask
- resist
- light shielding
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F1/00—Originals for photomechanical production of textured or patterned surfaces, e.g., masks, photo-masks, reticles; Mask blanks or pellicles therefor; Containers specially adapted therefor; Preparation thereof
- G03F1/38—Masks having auxiliary features, e.g. special coatings or marks for alignment or testing; Preparation thereof
- G03F1/46—Antireflective coatings
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F1/00—Originals for photomechanical production of textured or patterned surfaces, e.g., masks, photo-masks, reticles; Mask blanks or pellicles therefor; Containers specially adapted therefor; Preparation thereof
- G03F1/54—Absorbers, e.g. of opaque materials
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F1/00—Originals for photomechanical production of textured or patterned surfaces, e.g., masks, photo-masks, reticles; Mask blanks or pellicles therefor; Containers specially adapted therefor; Preparation thereof
- G03F1/60—Substrates
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F1/00—Originals for photomechanical production of textured or patterned surfaces, e.g., masks, photo-masks, reticles; Mask blanks or pellicles therefor; Containers specially adapted therefor; Preparation thereof
- G03F1/68—Preparation processes not covered by groups G03F1/20 - G03F1/50
- G03F1/76—Patterning of masks by imaging
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F1/00—Originals for photomechanical production of textured or patterned surfaces, e.g., masks, photo-masks, reticles; Mask blanks or pellicles therefor; Containers specially adapted therefor; Preparation thereof
- G03F1/68—Preparation processes not covered by groups G03F1/20 - G03F1/50
- G03F1/80—Etching
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
- H01L21/033—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising inorganic layers
- H01L21/0332—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising inorganic layers characterised by their composition, e.g. multilayer masks, materials
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
- H01L21/033—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising inorganic layers
- H01L21/0334—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising inorganic layers characterised by their size, orientation, disposition, behaviour, shape, in horizontal or vertical plane
- H01L21/0337—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising inorganic layers characterised by their size, orientation, disposition, behaviour, shape, in horizontal or vertical plane characterised by the process involved to create the mask, e.g. lift-off masks, sidewalls, or to modify the mask, e.g. pre-treatment, post-treatment
Abstract
[PROBLEMS] To provide a photomask substrate, a photomask, and a method of manufacturing the same, in which a fine pattern can be formed with high precision by wet etching.
In addition, the present invention includes a transparent substrate 10, a semi-transmissive layer 20 having a semi-transmissive, and a light shielding layer 33 formed on the semi-transmissive layer 20 to substantially shield irradiation light. In a photomask substrate 2, the semi-transmissive layer 20 is insoluble or poorly soluble in etching solution A than light shielding layer 33, and is soluble in etching solution B. Titanium (TiN x : where 0 <x <1.33). On the other hand, the light shielding layer 33 is more usable with respect to the etching liquid A than the semi-transmissive layer 20, and is formed with insoluble or poorly soluble metal chromium Cr. Since the etching resistance of each layer with respect to etching liquid differs, it becomes possible to selectively etch the transflective layer 20 and the light shielding layer 33 without damaging another layer.
Description
BACKGROUND OF THE INVENTION Field of the Invention The present invention relates to a substrate for a photomask, a photomask, and a method for manufacturing the same, having a semi-transmissive layer, and in particular, display elements and fine scattering irregularities of flat display devices such as LCDs, PDPs, and ELs, and the like. The present invention relates to a pattern forming photomask substrate, a photomask, and a method of manufacturing the same, which are used for surface modification such as antireflection plate, diffusion reflection plate with or without fine particles, microlens array, and other irregularities on the array.
With the development of liquid crystal display devices (reflective, transmissive and transflective), plasma display devices, organic electro-luminescence (EL) displays, and other flat panel display devices, the size, pattern, Various types of photomasks different from each other are used.
For example, in the formation of a liquid crystal display device, in the TFT (Thin Film Transistor) manufacturing step, depending on the manufacturing method, generally three to five photomasks for patterning are required. Moreover, also in the color filter side which is arrange | positioned facing a liquid crystal display element, the black mask formation, the color layer formation, and the photomask corresponding to a liquid crystal display element respectively are needed.
In photomasks used for forming fine patterns such as LSI, halftone masks are used for the purpose of improving pattern accuracy (for example, Patent Documents 1 to 9). The halftone mask is a photomask in which a transflective layer (halftone) is formed between the transmissive portion and the light shielding portion. This semi-transmissive layer is designed to have a film thickness such that the phase is inverted by? / 2 or shifted by? Λ / 4 in accordance with the exposure wavelength to be used. Accordingly, diffraction of light generated between adjacent patterns is prevented, and the difference in light intensity between the edge portion and the transmissive portion of the mask light shielding portion becomes clear. In addition, since moire and halation are less likely to occur, resolution can be improved. In addition, there is also a method (gray tone mask) which obtains the same effect as halftone by forming a fine continuous stripe pattern.
As a method of manufacturing such a halftone-mounted photomask, patterning is performed once by coating and exposing a resist to a photomask substrate (a photomask blank) on which a first layer (a semi-transmissive layer or a light shielding layer) is formed for the first time. The method of removing and cleaning a resist, forming a 2nd layer (shielding layer or semi-transmissive layer) again using a vacuum apparatus, etc., and then patterning the 2nd layer formed second in the photolithography process is known (for example, For example, refer patent document 3, 9). Moreover, as another manufacturing method, the method of first forming the thin film which has a homogeneous or heterogeneous multilayered structure, and then forming each pattern by dry etching is also known (for example,
Patent Document 1: Japanese Patent Application Laid-open No. Hei 7-209849
Patent Document 2: Japanese Patent Application Laid-Open No. 9-127677
Patent Document 3: Japanese Patent Application Laid-Open No. 2001-27801
Patent Document 4: Japanese Patent Application Laid-Open No. 2001-83687
Patent Document 5: Japanese Patent Application Laid-Open No. 2001-312043
Patent Document 6: Japanese Patent Application Laid-Open No. 2003-29393
Patent Document 7: Japanese Patent Application Laid-Open No. 2003-322949
Patent Document 8: Japanese Patent Application Laid-Open No. 2004-29746
Patent Document 9: Japanese Patent Publication No. 2006-18001
Disclosure of the Invention
Problems to be Solved by the Invention
In this conventional method, after patterning the first layer formed using a vacuum apparatus or the like, it is necessary to form the second layer using a vacuum apparatus or the like and patterning again. It is necessary to perform the film-forming process using an apparatus etc. twice or more. For this reason, there existed a problem that the process required for manufacturing a photomask increased, and the manufacturing cost rose.
In addition, the pattern formation of a photomask is usually carried out by dry etching which irradiates ions to the layer on the photomask substrate by plasma or laser light, such as a reactive gas, and wet which chemically corrodes the layer with a corrosive etching liquid (chemical). There are two types of etching methods of etching (also called wet etching). Among these, the dry etching method is generally used for the pattern formation of a photomask.
However, in dry etching, there are various technical problems associated with the enlargement of the photomask and the mass production. For example, in the direct drawing process in dry etching, the drawing area increases with an increase in the size of the photomask, so that an increase in drawing time by an electron beam, a laser, or the like occurs, and it is difficult to improve the tact time of photomask manufacturing. . In addition, with the increase in the size of the photomask, facilities such as vacuum tanks and gas type switching devices need to be increased in size, resulting in an increase in burden on equipment and an increase in the cost of manufacturing the photomask. . In addition, since the number of substrates that can be processed at one time is limited, it is not suitable for mass production.
On the other hand, in wet etching, since equipment and etching liquid are generally inexpensive, and the pattern formation by etching is possible in a short time rather than dry etching, compared with dry etching, large-size photomask production, photomask production, and a short time are performed. It is suitable for the production of.
However, in the wet etching, when etching any one of the laminated layers, a part of the other layer is dissolved, or the material and the etching solution react with the material constituting the other layer at the grain boundary of the other layer. By chemically altering to a heterogeneous structure, damage may be caused to other layers, which makes it difficult to process high precision. In particular, when manufacturing a mask in which different kinds of layers are laminated, such as a halftone mask in which a phase shift layer and a light shielding layer are laminated, it is technically difficult to selectively etch only a target layer without damaging other layers.
SUMMARY OF THE INVENTION In view of the above problems, an object of the present invention is to provide a photomask substrate capable of forming two kinds of fine patterns on the surface of a transparent substrate in a short time and at a low cost by a wet etching method which has been difficult with conventional photomask manufacturing techniques. It is in doing it.
Another object of the present invention is to provide a photomask having two kinds of fine patterns formed in a short time and at low cost by sequentially etching the substrate for photomask by wet etching, and a manufacturing method thereof.
Means to solve the problem
According to the photomask substrate of the present invention, a transparent substrate, a first layer formed on the transparent substrate and semi-transparent to the irradiation light, and formed on the first layer to substantially shield the irradiation light A light shielding portion in which the light shielding pattern formed by the second layer is exposed on the surface, a semi-transmissive portion in which the semi-transmissive pattern formed by the first layer is exposed on the surface, and the transparent substrate. A photomask substrate capable of forming a transparent portion exposed to the surface, wherein the first layer is insoluble or poorly soluble in the first etching solution than the second layer and is soluble in the second etching solution. The second layer is solved by being more soluble in the first etching solution than the first layer and insoluble or poorly soluble in the second etching solution.
As described above, according to the photomask substrate of the present invention, the first layer is insoluble or poorly soluble in the first etching solution than the second layer, and is soluble in the second etching solution, while the second layer is first in the first layer. It is soluble in the etchant and insoluble or poorly soluble in the second etchant. Thereby, a 2nd layer can be selectively etched using a 1st etching liquid, and a 1st layer can be selectively etched using a 2nd etching liquid.
By selectively etching the first layer and the second layer with different etching solutions, two kinds of patterns, a transflective pattern and a light shielding pattern, are formed on the transparent substrate, and the light shielding portion where the light shielding pattern is exposed and the semitransmissive pattern are formed on the surface. It is possible to form three regions of the exposed semi-transmissive portion and the transparent portion in which the transparent substrate is exposed on the surface by wet etching using an etching solution.
As described above, in the photomask substrate of the present invention, the first layer and the second layer each have resistance to different etching liquids, and by using the difference in resistance, the first layer is prepared by the second etching liquid solubilizing the first layer. The two layers are hardly modified or damaged, and conversely, the first layer is hardly modified or damaged by the first etchant that solubilizes the second layer. Thereby, it becomes possible to manufacture the photomask in which the precision is high and a fine pattern was formed.
In addition, the first layer is preferably formed directly on the transparent substrate.
In general, a metal compound layer or the like is interposed between the transparent substrate and the first layer in order to improve the adhesion between them. However, by directly forming the first layer on the transparent substrate, there is no need to interpose the metal compound layer. As a result, it is possible to reduce the number of processes for forming the metal compound layer on the surface of the transparent substrate and the material therefor, thereby improving the production efficiency of the photomask substrate.
In addition, the first layer is preferably formed on the transparent substrate via a metal compound layer having a transmittance of 70% or more and less than 100%.
In this way, the first layer is formed on the transparent substrate through a metal compound layer having a transmittance of 70% or more and less than 100%, thereby improving the adhesion between the transparent substrate and the first layer with almost no reflection of light passing through the transparent substrate. In addition, it is also possible to protect the surface of the transparent substrate from damage caused by the etching solution during photomask fabrication.
At this time, the refractive index of the metal compound layer is more preferably equal to the refractive index of the substrate or lower than the refractive index of the substrate.
In addition, the first etching solution is preferably a mixed solution of cerium ammonium nitrate, perchloric acid and water.
In addition, the second etching solution is preferably a mixture of potassium hydroxide, hydrogen peroxide and water.
In addition, the first layer is preferably composed of one or two or more components selected from the group consisting of titanium, titanium nitride and titanium oxynitride as main components.
In addition, the second layer is suitably composed of one or two or more components selected from the group consisting of chromium, chromium oxide, chromium nitride and chromium nitride.
By appropriately selecting the first etching solution, the second etching solution, the first layer and the second layer in this way, the selectivity of the etching solution for each layer can be improved, and a more accurate and finer pattern can be formed.
In particular, one or two or more components selected from the group consisting of titanium, titanium nitride and titanium oxynitride are insoluble or poorly soluble in the mixed solution of cerium ammonium nitrate, perchloric acid and water as the first etching solution, potassium hydroxide, hydrogen peroxide and It is usable for the mixed liquid of water. On the other hand, one or two or more selected from the group consisting of chromium, chromium oxide, chromium nitride and chromium oxynitride are usable for a mixed solution of cerium ammonium nitrate, perchloric acid and water as the first etching solution, and potassium hydroxide, hydrogen peroxide and the second etching solution. It is insoluble or poorly soluble in the mixed solution of water.
As a result, by employing titanium or a titanium compound as the first layer and chromium or a chromium compound as the second layer, the selectivity to each etching solution can be improved, and a highly precise and fine pattern can be formed.
In particular, titanium nitride is highly resistant to chemicals such as acids and alkalis, and therefore is hardly damaged by chemicals used in etching processes such as resist removal liquids. As a result, it is possible to perform selective etching smoothly and to form a fine pattern with high accuracy.
Moreover, it is preferable that a said 2nd layer is equipped with the light shielding layer and the reflection prevention layer formed in the surface side rather than this light shielding layer.
Thus, since the 2nd layer is equipped with the antireflection layer, since an antireflection effect can be acquired and halation etc. by reflection of irradiation light at the time of mask exposure are prevented, it is preferable.
In addition, since the second layer is formed of the light shielding layer and the antireflection layer, the light shielding layer and the antireflection layer can be etched collectively, and the light shielding pattern having the antireflection layer pattern formed on the surface can be easily formed.
In this case, the anti-reflection layer is suitable as long as it is a layer composed mainly of one or two or more components selected from the group consisting of chromium oxide, chromium nitride and chromium nitride.
As described above, since the antireflection layer is formed of a layer composed mainly of one or two or more components selected from the group consisting of chromium oxide, chromium nitride and chromium nitride having low reflectance, a high antireflection effect is obtained and at the time of mask exposure. It is preferable because halation or the like due to reflection of the irradiation light is prevented.
In addition, the first layer is a layer composed mainly of one or two or more components selected from the group consisting of chromium, chromium oxide, chromium nitride and chromium nitride, and the second layer is a group consisting of titanium, titanium nitride and titan oxynitride The first etching solution is a mixture containing potassium hydroxide, hydrogen peroxide and water, and the second etching solution is a mixed solution of cerium ammonium nitrate, perchloric acid and water, by the same operation as described above. The selectivity with respect to each etching liquid improves, and it becomes possible to form a more precise and fine pattern.
Further, the first layer and the second layer are preferably formed by sputtering, ion plating or vapor deposition.
As described above, since the first layer and the second layer are manufactured by a film formation technique such as sputtering, the film thickness can be appropriately adjusted to form a photomask substrate having the desired optical characteristics. It is possible to form a photomask having characteristics. Moreover, by manufacturing by film-forming techniques, such as a sputtering method, it becomes possible to adjust physical properties, such as chemical-resistance and fastness of a photomask substrate, suitably.
According to the photomask of the present invention, a transparent substrate, a first layer formed on the transparent substrate and semi-transparent to the irradiation light, and a first layer formed on the first layer to substantially shield the irradiation light A photomask formed by a substrate for photomasks having two layers,
The first layer is insoluble or poorly soluble in the first etching solution than the second layer, and is soluble in the second etching solution, and the second layer is more soluble in the first etching solution than the first layer, Insoluble or poorly soluble in an etching solution, the photomask includes a light shielding portion on which a light shielding pattern formed by etching the second layer by the first etching solution is exposed to the surface, and the first layer is etched by the second etching solution. And a transflective portion through which the formed semitransmissive pattern is exposed on the surface, and the second layer and the first layer are etched by the first etchant and the second etchant, respectively, to form a transparent portion on which the transparent substrate is exposed. It is solved by being.
As described above, according to the photomask of the present invention, the first layer is insoluble or poorly soluble in the first etching solution than the second layer and is soluble in the second etching solution, while the second layer is the first etching solution rather than the first layer. It is soluble in water and insoluble or poorly soluble in the second etching liquid. Thereby, a 2nd layer can be selectively etched using a 1st etching liquid, and a 1st layer can be selectively etched using a 2nd etching liquid.
Then, by selectively etching the first layer and the second layer with different etching solutions, two kinds of patterns of light shielding patterns and semi-transmissive patterns are formed on the transparent substrate, and the light shielding portions where the light shielding patterns are exposed and the semi-transmissive patterns are surfaced. The three types of regions of the transflective portion exposed to the transparent portion exposed to the surface and the transparent substrate exposed to the surface are formed on the surface of the transparent substrate by wet etching using an etching solution.
Thus, according to the photomask of this invention, since the difference of the tolerance with respect to the etching liquid of a 1st layer and a 2nd layer is utilized, the 2nd layer is hardly modified or damaged by the etching liquid of a 1st layer, On the contrary, the first layer is hardly modified or damaged by the etching solution of the second layer, so that it is possible to provide a photomask having a high degree of fine pattern.
According to the above-described method for manufacturing a photomask, the above-described problem is achieved by a first resist coating step of coating a resist on a surface of the second layer and a first resist coating step by using a mask on which a first mask pattern is formed. A first exposure step of exposing the coated resist, a first resist removal step of removing an exposed portion of the resist after the first exposure step, and the second layer exposed in a region from which the resist is removed; A first etching step of etching the first etching solution to form the light shielding pattern, a first resist stripping step of peeling the resist remaining in the first resist removing step, and a second resist coating the resist on the surface again Exposure of the resist coated in the second resist coating step via a coating step and a mask having a second mask pattern formed thereon; Performing a second exposure step, a second resist removal step of removing an exposed portion of the resist after the second exposure step, and etching the first layer exposed to the region from which the resist is removed with the second etching solution. This is solved by performing a second etching step of forming the semi-transmissive pattern and a second resist peeling step of peeling the resist remaining in the second resist removing step.
Thus, according to the photomask manufacturing method of this invention, a resist is exposed using the mask in which the 1st mask pattern was formed, the exposed part of the resist was removed, the 2nd layer was etched with a 1st etching liquid, A plurality of pattern formation regions can be formed on the surface of the transparent substrate by exposing the resist with a mask on which two mask patterns are formed, removing the exposed portion of the resist, and etching the first layer with a second etching solution.
That is, by using the difference in the resistance to the etching solution of the first layer and the second layer, it is possible to form a fine pattern with high accuracy with little modification or damage by the etching solution used for etching other layers.
Effects of the Invention
According to the photomask substrate of the present invention, since the second layer can be selectively etched by the first etching liquid and the first layer by the second etching liquid, the first layer and the second layer are modified or damaged by the etching liquid of each other. It is possible to manufacture a photomask having a high degree of precision and a fine pattern formed by wet etching, which is hardly conventionally received.
In addition, according to the photomask of the present invention and a method for manufacturing the same, the first layer and the first layer can be selectively etched by the second etching solution, so that the first layer and the second layer are applied to each other's etching solution. This makes it possible to hardly modify or damage, thereby forming a photomask having a high degree of fine pattern by wet etching, which is conventionally difficult.
Therefore, according to the present invention, since the patterning can be performed by wet etching suitable for the production of large-scale photomasks or the mass production of photomasks, the photomasks can be produced in a short time and at a low cost as compared with the conventional patterning by dry etching. It becomes possible.
Brief description of the drawings
1 is a longitudinal cross-sectional view of a substrate for a photomask of one embodiment of the present invention.
2 is a longitudinal cross-sectional view of the photomask of one embodiment of the present invention.
3 is an explanatory diagram showing a step of patterning a photomask from a photomask substrate.
4 is an explanatory diagram showing a step of patterning a photomask.
It is a longitudinal cross-sectional view of the photomask board | substrate of other embodiment of this invention.
FIG. 6 is an electron microscope photograph of the end face and the plane of the photomask after the light shielding pattern is formed. FIG.
7 is an optical microscope photograph of a plane after cross pattern formation.
8 is an electron microscope photograph of the longitudinal section and the plane of the photomask after the transflective pattern is formed.
Explanation of the sign
1 ‥ Photomask
2 ‥ Photomask Substrate
1a ‥ Shading part
1b ‥ semi-permeable part
1c ‥ transparent part
10 ‥ transparent substrate
20 ‥ semi-permeable layer (first layer)
20a ‥ transflective pattern
30 ‥ Composite Layer (2nd Layer)
30a ‥ shading pattern
33 ‥ shading layer
33a ‥ Shading layer pattern
35 ‥ Antireflection layer
35a ‥ antireflection layer pattern
50 ‥ Resist
60 ‥ mask disc
70 ‥ Resist
80 ‥ mask disc
90 ‥ metal compound layer
Implement the invention Best form for
EMBODIMENT OF THE INVENTION Hereinafter, one Embodiment of this invention is described with reference to drawings. In addition, the member, arrangement | positioning, order, etc. which are demonstrated below do not limit this invention, Of course, it can be variously modified according to the meaning of this invention.
1 is a longitudinal cross-sectional view of a photomask substrate of one embodiment of the present invention, FIG. 2 is a longitudinal cross-sectional view of a photomask of one embodiment of the present invention, and FIG. 3 is a step of patterning a photomask from a photomask substrate. 4 is an explanatory view showing a step of patterning a photomask, FIG. 5 is a longitudinal cross-sectional view of a photomask substrate according to another embodiment of the present invention, and FIG. 6 is a longitudinal cross section and a plane of a photomask after light shielding pattern formation. 7 shows an electron microscope photograph of the photomicrograph, and FIG. 7 shows an optical microscope photograph of the plane after the cross pattern formation, and FIG. 8 shows an electron microscope photograph of the longitudinal section and the plane of the photomask after the transflective pattern formation. In addition, in FIG. 1-5, the manufacturing process of the photomask board | substrate, photomask, and photomask is shown typically by drawing the film thickness of each layer thicker than actual thickness, in order to make understanding of invention easy.
As shown in Fig. 1, the photomask substrate (also referred to as a photomask blank) 2 of this example includes a
As shown in FIG. 2, the photomask 1 of this example is formed in the
The photomask 1 has a part of the
Transparent board (10)
Below, each member which comprises the
The
(Transmissive layer 20)
The
A film having such optical properties is possible by thinning a dielectric material based on wave optical theory, but considering the patterning property, the film is necessarily preferred from the viewpoint of selectivity to etching solution, adhesion to resist material, tact time, pattern degree, and the like. Can not. Therefore, it is preferable that the
Examples of the material having such characteristics include oxides, nitrides, and oxynitrides of metals. In addition, also in the
The
That is, the
In this way, the
In this case, the
In contrast, the fact that the
Further, even when the
In contrast, the fact that the
Specifically, in the present embodiment, when the substrate is immersed in the etching solution A for 30 ° C. for about 70 seconds (that is, the time when the
In addition, when immersed in etching liquid B for 30 second and 120 second (that is, time which can fully etch the transflective layer 20), the optical density of the
Thus, since the solubility of the
The inventors investigated the solubility of oxides, nitrides, and oxynitrides of several metals in etching solution A (a mixture of cerium ammonium nitrate, perchloric acid and water) and etching solution B (a mixture of potassium hydroxide, hydrogen peroxide, and water). Metals used are nickel, titanium, tantalum, aluminum, molybdenum and copper.
As a result, any of oxides, nitrides, and oxynitrides was soluble in the etching solution A for nickel, molybdenum, and copper, and insoluble in the etching solution B. As a result, it was found to be unsuitable for use in the selective etching with the
In addition, as a result of investigating the oxides, nitrides, and oxynitrides of aluminum, tantalum, and titanium, it was found that the etching solution A was insoluble in all, but the titanium nitride and the titanium oxynitride were soluble in the etching solution B.
Moreover, about these compounds, the pattern formation by the etching was performed and the pattern grade was investigated individually. As a result, it was found that oxides of tantalum, nitrides, oxynitrides, oxides of aluminum, and oxides of titanium are not suitable for wet etching because patterns cannot be formed or the pattern degree is low.
From the results of the investigation, the selection of the etching solution and the patternability of the titanium nitride (TiN x ) film having etching resistance and optical characteristics with respect to the etching solution A were examined. First, as a result of repeating the examination of the solubility and etching property of various chemicals, the titanium nitride (TiN x ) film has an alkali (eg, potassium hydroxide (KOH)) resistance in the photolithography process, but also hydrogen peroxide (H 2). It was found that soluble in O 2 ), a mixture of potassium hydroxide (KOH) and water, and further fine patterning is possible, that is, titanium nitride (TiN x ) has a light shielding in addition to the properties that can be made into the desired optical properties It was found that it was resistant to the etching solution A solubilizing the
Next, the adhesion of the
The adhesiveness of the
Thus, titanium nitride (TiN x ) has optical characteristics, resistance to etching solution A (insoluble or poorly soluble), and solubility (soluble) in etching solution B, and also has good adhesion to the
(Shading Layer 33)
Next, the
The
(Anti-reflective layer 35)
Next, the
In the present invention, the
The
The left column (refractive index) of this table shows the refractive index with respect to the irradiated light of the
In addition, the uranium (reflectivity) represents the relative characteristic of the reflectance, "↓" represents a low reflectance, "→" represents a medium reflectance, and "↑" represents a high reflectance. In addition, in this column, evaluation according to the height of an antireflection effect is shown by the symbol of "x", "(triangle | delta)", and "(circle)" in order from a low effect to a high order.
The following can be said from this table.
The material having less absorption for irradiated light than the
The material having less absorption for irradiated light than the
On the other hand, a material satisfying the following requirements has a low antireflection effect or almost no antireflection effect.
The material having less absorption for irradiated light than the
As described above, the
In fact, since each of the
In addition, when the absorption of the
The
As the material of the
Next, the manufacturing method of the photomask 1 of this invention is demonstrated.
The photomask 1 of the present invention comprises a
In the case of film formation by sputtering, reactive sputtering can be used in addition to the usual sputtering. One of the reactive sputtering apparatuses is a device having a film formation region for sputtering a target and a reaction region for plasma treatment of the thin film after film formation with plasma of a reactive gas. The second is a conventional sputtering apparatus, which introduces a reactive gas during film formation and promotes the reaction using plasma by sputtering. Hereinafter, a film is formed by the second reactive sputtering apparatus, titanium nitride (TiN x ) as the
(Film Forming Process)
First, the
Next, the
Next, the
In the same way as when forming titanium nitride, metal chromium is used as a target. After the
When the
Next, the
Patterning process
The predetermined pattern is formed using the photolithography technique and the etching technique with respect to the
First, the
Next, the mask pattern is formed in the resist 50 using the mask
Next, the resist 50 after exposure is immersed in a developing solution. Thereby, the area | region which was exposed to the ultraviolet-ray in the resist 50 is removed with the developing solution, and the
Next, the
On the other hand, the
Next, the resist 50 remaining on the surface is dissolved with a release agent, and the surface is washed with pure water or the like (Fig. 3 (f)). As a result, the same pattern as the first mask pattern remains on the surface of the transparent substrate 10 (first resist stripping step).
Next, the resist 70 is apply | coated to the surface and it temporarily hardens (FIG. 4 (b)). The resist 70 may be made of the same material as that of the previous resist 50, or may be made of a material having different curing performance and the like. As a result, the resist 70 is coated on the surface (second resist coating step).
Subsequently, a mask pattern is formed in the resist 70 using the mask
Next, the resist 70 after exposure is immersed in a developing solution, and the area | region which was exposed to the ultraviolet-ray among the resists 70 is removed (FIG. 4 (d)). As a result, part of the resist 70 is removed, and the same pattern as the second mask pattern is formed by the remaining resist 70 (second resist removing step).
Next, the
On the other hand, since the
Finally, the resist 70 remaining on the surface is dissolved with a release agent, and the surface is washed with pure water or the like (Fig. 4 (f)). As a result, the same pattern as the second mask pattern remains on the surface of the transparent substrate 10 (second resist stripping step).
When etching is performed by this method, as shown in FIG. 2, the part which is not exposed by the 1st mask pattern does not etch any of the
The photomask 1 manufactured in this way can be used as a multi-tone mask used for manufacturing a TFT panel or the like. In a manufacturing process such as a TFT panel, a transfer substrate is provided so as to face the surface side (the
In this way, by using the photomask 1 of the present invention as a pattern transfer mask in photolithography technology, a plurality of transfer patterns having different exposure intensities can be easily formed. In addition, the variation of exposure can be further increased by changing the wavelength and intensity of the light to be irradiated.
In addition, the
On the other hand, as shown in FIG. 5, the
The
The
In addition, in description of the said embodiment, etching liquid A (mixture liquid of cerium ammonium nitrate, perchloric acid, and water) which is a 1st etching liquid, etching liquid B (mixture liquid of potassium hydroxide, hydrogen peroxide, and water) which is a 2nd etching liquid, and the 1st layer which has semipermeability (A layer mainly composed of titanium nitride), a second layer (chromium layer) that substantially shields irradiation light, and an antireflection layer (chromium oxide layer), but the material of the first layer and the material of the second layer have been described. The same effect and effect can be acquired also when the is substituted and the 1st etching liquid and the 2nd etching liquid are substituted.
That is, the first layer is composed of one or two or more components selected from the group consisting of chromium, chromium oxide, chromium nitride and chromium nitride, and the second layer is composed of titanium, titanium nitride and titanic nitride. Let it be a layer which has 1 or 2 or more components chosen as a main component. Then, a mixed solution of potassium hydroxide, hydrogen peroxide and water is used as the first etching solution, and a mixed solution of cerium ammonium nitrate, perchloric acid and water is used as the second etching solution. Also in this case, the same effect and effect as the above embodiment can be obtained.
Hereinafter, the manufacturing method of the photomask 1 using the
(Example 1)
In this embodiment, each layer on the surface of the
In this example, a quartz substrate (transparent substrate 10) was first set in a sputtering apparatus, and reactive sputtering was performed using a commercially available metal titanium target (purity of 99.99% or more). In the sputtering step, the
In addition, the target at this time is not limited to the thing which used the metal titanium target like this example, The thing which bonded the sintered compact of titanium nitride may be sufficient. In addition, since the degree of nitriding varies depending on the apparatus, it may be adjusted by appropriately combining the film forming conditions.
Next, the metal titanium target was changed into a metal chromium target, and the
Subsequently, the target was changed into another new metal chromium target, and the
The general reflectance at this time is 25 to 30% at the wavelength of 650 nm and at least 6 to 8% in the vicinity of 430 nm when the
Next, the
After resist temporary curing, exposure of 2nd stripe pattern (Ok manufacturing company jet printer: light source CHM-2000 ultra-high pressure mercury lamp exposure for 16 second), image development (Tokyo Oka Corporation PMER developer:
Since the overetch dimension of the
Among these, the cross-sectional observation results of (a) and (b) show that the
Next, the substrate after removing the resist was rotated 90 degrees, and the resist was applied to the entire surface to be temporarily cured. Subsequently, exposure of the first stripe pattern (Ok manufacturing company jet printer: light source CHM-2000 ultra-high pressure mercury lamp for 16 seconds), development (Tokyo Oka Co., Ltd. PMER developer:
7 shows an example in which the patterning is performed such that the line width of the pattern is 5 占 퐉, and an example in which the patterning is performed so that the line width is 2 占 퐉 is shown. The lower straight line pattern (longitudinal straight line) of each photograph is the
From the photograph of FIG. 7, it turns out that each pattern has favorable linearity even if the line width is short as 2 micrometers. Therefore, according to the manufacturing method of the photomask of this invention, it turned out that it is possible to form a fine pattern with high precision.
Next, the board | substrate was cut | disconnected longitudinally and the cross section and plane were observed with the electron microscope similarly to the case where the overetch dimension was measured after formation of the
Among these, it can be seen from the results of the cross-sectional observation in FIGS. 8A and 8B that the
Using another substrate not patterned, the optical density (OD) was measured with a Macbeth densitometer manufactured by Konishiroku Photo Co., Ltd., and the
By using a part of the cross pattern, the
(Example 2)
Unlike Example 1, Example 2 is an example in which the
In accordance with the same procedure as in Example 1, the
Next, the
As in Example 1, the transmittance and the like were measured, and the optical concentration was 3.29, and the transmittance was 12.85% at 350 nm, 21.14% at 436 nm, and 25.53% at 500 nm.
In addition, as a result of the film thickness measurement, the film thickness of the
(Example 3)
Unlike Example 1 and 2, Example 3 is the example which designed the
In accordance with the same procedure as in Example 1, the
Next, the
As in Example 1, the transmittance and the like were measured, and the optical concentration was 3.22, and the transmittance was 18.79% at 350 nm, 29.67% at 436 nm, and 32.78% at 500 nm.
Moreover, as a result of the film thickness measurement, the film thickness of the
(Example 4)
Unlike Example 1-3, Example 4 is the example which designed the
In accordance with the same procedure as in Example 1, the
Next, the
As in Example 1, the transmittance and the like were measured, and the optical concentration was 3.17, and the transmittance was 28.05% at 350 nm, 39.93% at 436 nm, and 48.18% at 500 nm.
In addition, as a result of the film thickness measurement, the film thickness of the
(Example 5)
Unlike Example 1-4, Example 5 is the example which designed the
In accordance with the same procedure as in Example 1, the
Next, the
As in Example 1, the transmittance and the like were measured, and the optical concentration was 3.03 and the transmittance was 40.01% at 350 nm, 52.03% at 436 nm, and 59.59% at 500 nm.
Moreover, as a result of the film thickness measurement, the film thickness of the
(Example 6)
Unlike Example 1-5, Example 6 is the example which designed the
In accordance with the same procedure as in Example 1, the
Next, the
As in Example 1, the transmittance and the like were measured, and the optical concentration was 3.13, and the transmittance was 48.06% at 350 nm, 60.52% at 436 nm, and 68.30% at 500 nm.
Moreover, as a result of the film thickness measurement, the film thickness of the
The patterning property of the
In addition, it is estimated that the linearity of pattern etch is impaired by reaction with the etching liquid in a thin film grain boundary, or lack of adhesiveness in a thin film and resist interface by patterning without surface treatment. This lack of adhesion is considered to be caused by oxidation, contamination of the surface of the thin film by leaving the
(Example 7)
In the present embodiment, unlike Examples 1 to 6, the material of the first layer (semi-transmissive layer) and the material of the second layer (shielding layer) are replaced, and the first etching liquid (etching liquid A) and the second etching liquid ( It is an example when the etching liquid B) is substituted. In addition, the film-forming process and the patterning process are basically the same procedure as Example 1-6.
In the same manner as in Example 1, a quartz substrate (transparent substrate 10) was first set in a sputtering apparatus, and reactive sputtering was carried out using a commercially available chromium metal target (purity of 99.99 or more). In the sputtering step, the
Next, the metal chromium target was changed into the metal titanium target, and the
Next, the target was changed to a new titanium target, and the
The reflectance at this time is 35 to 38% at the wavelength of 650 nm and 9 to 10% at the vicinity of 430 nm when the
Next, the
The board | substrate after formation was cut | disconnected longitudinally, the electron microscope photograph similar to FIG. 6 of Example 1 was taken, and the cross section and the plane were observed. From the results of the cross-sectional observation, it was found that the overetch dimension was 0.39 m. Moreover, it turned out that the unevenness generate | occur | produces in the edge part of a linear pattern, and the maximum and minimum width are 0.1 micrometer or less from the result of frontal observation. At this point in time, no change was observed in the chromium oxynitride (CrON) film, which is the
Next, the
As in Example 1, the transmittance and the like were measured, and the optical concentration was 3.07, and the transmittance was 7.65% at 350 nm, 18.97% at 436 nm, and 27.66% at 500 nm.
In addition, as a result of the film thickness measurement, the film thickness of the
(Example 8)
Unlike Example 7, Example 8 is an example in which the
According to the same procedure as in the seventh embodiment, a stripe pattern consisting of the
Next, the
As in Example 1, the transmittance and the like were measured, and the optical concentration was 3.05 and the transmittance was 29.03% at 350 nm, 37.66% at 436 nm, and 43.48% at 500 nm.
Moreover, as a result of the film thickness measurement, the film thickness of the
(Example 9)
Unlike Example 7, 8, Example 9 is the example which designed the
According to the same procedure as in Examples 7 and 8, a stripe pattern consisting of the
Next, the
As in Example 1, the transmittance and the like were measured, and the optical concentration was 3.03 and the transmittance was 48.21% at 350 nm, 59.05% at 436 nm, and 64.98% at 500 nm.
Moreover, as a result of the film thickness measurement, the film thickness of the
As shown in these Examples 7-9, even when the material of the semi-transmissive layer which is a 1st layer, and the material of the light shielding layer which is a 2nd layer is substituted, and the etching liquid A which is a 1st etching liquid and the etching liquid B which is a 2nd etching liquid are substituted, The same results as in Examples 1 to 6 were obtained.
As a result, it was confirmed that not only the black matrix used in the liquid crystal display element, the color filter substrate, etc., but also as a photomask can be sufficiently used. Table 2 shows the evaluation results of Examples 1-9.
Below, a comparative example is demonstrated.
(Comparative Example 1)
Comparative Example 1 Example 1-9 unlike the
In Comparative Example 1, the same sputtering apparatus as in Example 1 was used, the metal titanium target of Example 1 was replaced with a metal chromium target (purity of 99.99% or more), oxygen gas was used as the reactive gas, and reactive sputtering Chromium oxide (CrO x ) as the first antireflection layer was directly deposited on the surface of the
Next, the metal chromium target was changed into a new metal chromium target, and a light shielding layer of metal chromium (Cr) was formed on the surface of the first antireflection layer by sputtering. This light shielding layer has a film thickness capable of shielding almost 100% (OD> 3.0) against the irradiation light. Further, a second antireflection layer made of chromium oxide (CrO x ) was formed on the surface of the light shielding layer successively.
Subsequently, the laminated substrate formed in the said sputtering process was taken out of the sputtering apparatus, and left to stand for one week in the storage. Subsequently, ultrasonic cleaning was performed on each of a plurality of sets of alkaline detergents, neutral detergents, and pure water on the substrate taken out from the storage, and then the same resist as in Example 1 was applied to the entire surface of the substrate to perform temporary curing. Thereafter, exposure, development, and main curing were performed using the pattern used in Example 1, and the first antireflection layer, the light shielding layer, and the second antireflection layer were prepared using a mixed solution of perchloric acid, cerium ammonium nitrate, and water as the first etching solution. It etched collectively and the stripe pattern was formed.
By observing the cross section and the plane using an electron microscope in the same manner as in Example 1, the overetch of the stripe pattern consisting of three layers at this time was evaluated. As a result, it was found from the cross-sectional observation that the overetch dimension was 0.40 µm, and from the results of the front observation, the width of the unevenness in the edge portion of the linear pattern was 0.1 µm or less.
Using other substrates without patterning, optical density (OD) and spectral reflectance, which are optical characteristics, were measured in the same manner as in Example 1 with a magnetic spectrophotometer U-4000 manufactured by Hitachi High Technologies. The resultant optical density was 3.18, and the reflectance from the substrate surface side was 7.11% at 436 nm.
Moreover, when the film thickness of the pattern which becomes a 1st anti-reflective layer, a light shielding layer, and a 2nd anti-reflective layer was measured using a part of etched stripe pattern, these total film thickness was 1280 Pa (128.0 nm). The results are shown in Table 2.
(Comparative Example 2)
In Comparative Example 2, unlike Examples 1 to 9 and Comparative Example 1, two layers of a chromium oxide (CrO x ) layer as an antireflection layer and a metal chromium (Cr) layer as a light shielding layer are formed on the surface of the
In this example, chromium oxide (CrO x ) was laminated so as to have a film thickness of 300 kPa (30.0 nm) in the same procedure as in Example 1. Subsequently, metal chromium (Cr) was deposited thereon to have a film thickness of 700 kPa (70.0 nm).
Next, exposure, development, and main curing were carried out in the same manner as in Example 1, and the chromium oxide (CrO x ) layer and the metal chromium (Cr) layer were collectively combined using a mixed solution of perchloric acid, cerium ammonium nitrate, and water as the first etching solution. Etching was performed to form a stripe pattern.
By observing the cross section and the plane using an electron microscope in the same manner as in Example 1, the over-etch of the stripe pattern including the chromium oxide (CrO x ) layer as the antireflection layer and the metal chromium (Cr) layer as the light shielding layer was evaluated. . As a result, it was found from the cross-sectional observation that the overetch dimension was 0.38 µm, and from the results of the front observation, the width of the unevenness in the edge portion of the linear pattern was 0.1 µm or less.
Using other substrates without patterning, optical density (OD) and spectral reflectance, which are optical characteristics, were measured in the same manner as in Example 1 with a magnetic spectrophotometer U-4000 manufactured by Hitachi High Technologies. The resultant optical density was 3.04, and the reflectance from the substrate surface side was 7.53% at 436 nm.
Moreover, when the film thickness of the pattern used as a light shielding layer and an antireflection layer was measured using a part of etched stripe pattern, these total film thickness was 980 kPa (98.0 nm). The results are shown in Table 2.
(Comparative Example 3)
In Comparative Example 3, unlike Examples 1 to 9 and Comparative Examples 1 and 2, only a chromium oxide (CrO x ) layer is formed on the surface of the
In this example, a chromium oxide (CrO x ) layer was formed so as to have a film thickness of 300 kPa (30.0 nm) in the same procedure as in Example 1.
Next, exposure, development, and main curing were performed in the same manner as in Example 1, and the chromium oxide (CrO x ) layer was etched using a mixed solution of perchloric acid, cerium ammonium nitrate, and water as the first etching solution to form a stripe pattern. .
By observing the cross section and the plane using an electron microscope in the same manner as in Example 1, the overetch of the pattern of the chromium oxide (CrO x ) layer at this time was evaluated. As a result, it was found from the cross-sectional observation that the overetch dimension was 0.38 µm, and from the results of the front observation, the width of the unevenness in the edge portion of the linear pattern was 0.1 µm or less.
Using other substrates without patterning, optical density (OD) and spectral transmittance, which are optical characteristics, were measured in the same manner as in Example 1 with a magnetic spectrophotometer U-4000 manufactured by Hitachi Hi-Technologies. The resultant optical density was 0.39, and the transmittance was 40.64% at 436 nm.
In addition, when the film thickness of the pattern was measured using a part of the etched stripe pattern, the film thickness was 290 kPa (29.0 nm). The results are shown in Table 2.
(Comparative Example 4)
In Comparative Example 4, unlike Examples 1 to 9 and Comparative Examples 1 to 3, only the metal chromium (Cr) layer is formed on the surface of the
In this example, a metal chromium (Cr) layer was formed so as to have a film thickness of 700 kPa (70.0 nm) in the same procedure as in Example 1.
Next, exposure, development, and main curing were performed in the same procedure as in Example 1, and the metal chromium (Cr) layer was etched using a mixed solution of perchloric acid, cerium ammonium nitrate, and water as the first etching solution to form a stripe pattern.
By observing the cross section and the plane using an electron microscope in the same manner as in Example 1, the over-etch of the pattern of the metal chromium (Cr) layer was evaluated at this time. As a result, it was found from the cross-sectional observation that the overetch dimension was 0.35 µm, and from the results of the frontal observation, the width of the unevenness in the edge portion of the linear pattern was 0.05 µm or less.
Using other substrates without patterning, optical density (OD) and spectral reflectance and transmittance, which are optical characteristics, were measured in the same manner as in Example 1 with a Hitachi Hi-Technologies magnetospectrophotometer U-4000. The resultant optical density was 3.02, the transmittance was 0.092% at 436 nm, and the reflectance was 59.71%.
Moreover, when the film thickness of the pattern was measured using a part of the etched stripe pattern, these total film thicknesses were 720 kPa (72.0 nm). The results are shown in Table 2.
Claims (13)
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CN113517188B (en) * | 2021-06-29 | 2024-04-26 | 上海华力集成电路制造有限公司 | Patterning process method using multi-layer mask plate |
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