CN110809735B - Photomask blank, photomask, exposure method, and device manufacturing method - Google Patents
Photomask blank, photomask, exposure method, and device manufacturing method Download PDFInfo
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- CN110809735B CN110809735B CN201880043992.2A CN201880043992A CN110809735B CN 110809735 B CN110809735 B CN 110809735B CN 201880043992 A CN201880043992 A CN 201880043992A CN 110809735 B CN110809735 B CN 110809735B
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- 239000000758 substrate Substances 0.000 claims abstract description 75
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 28
- 239000001301 oxygen Substances 0.000 claims abstract description 28
- 239000011651 chromium Substances 0.000 claims abstract description 22
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 21
- 239000010410 layer Substances 0.000 claims description 197
- 229920002120 photoresistant polymer Polymers 0.000 claims description 33
- 238000004519 manufacturing process Methods 0.000 claims description 31
- 238000000034 method Methods 0.000 claims description 14
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- 239000002344 surface layer Substances 0.000 claims description 5
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 claims description 3
- 238000004544 sputter deposition Methods 0.000 description 53
- 239000007789 gas Substances 0.000 description 19
- 238000005530 etching Methods 0.000 description 13
- 239000000463 material Substances 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 239000007788 liquid Substances 0.000 description 9
- 238000010586 diagram Methods 0.000 description 8
- 238000001039 wet etching Methods 0.000 description 8
- 238000005259 measurement Methods 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 230000004048 modification Effects 0.000 description 6
- 238000012986 modification Methods 0.000 description 6
- 229910052786 argon Inorganic materials 0.000 description 5
- 238000004140 cleaning Methods 0.000 description 5
- 230000000149 penetrating effect Effects 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 230000035515 penetration Effects 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 2
- XMPZTFVPEKAKFH-UHFFFAOYSA-P ceric ammonium nitrate Chemical compound [NH4+].[NH4+].[Ce+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O XMPZTFVPEKAKFH-UHFFFAOYSA-P 0.000 description 2
- 229910000423 chromium oxide Inorganic materials 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 238000005477 sputtering target Methods 0.000 description 2
- 239000003513 alkali Substances 0.000 description 1
- SJKRCWUQJZIWQB-UHFFFAOYSA-N azane;chromium Chemical compound N.[Cr] SJKRCWUQJZIWQB-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- UFGZSIPAQKLCGR-UHFFFAOYSA-N chromium carbide Chemical compound [Cr]#C[Cr]C#[Cr] UFGZSIPAQKLCGR-UHFFFAOYSA-N 0.000 description 1
- 230000001427 coherent effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001312 dry etching Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 238000001659 ion-beam spectroscopy Methods 0.000 description 1
- 238000010884 ion-beam technique Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 238000000206 photolithography Methods 0.000 description 1
- 238000001552 radio frequency sputter deposition Methods 0.000 description 1
- 229910003470 tongbaite Inorganic materials 0.000 description 1
Images
Classifications
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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
- G03F1/58—Absorbers, e.g. of opaque materials having two or more different absorber layers, e.g. stacked multilayer absorbers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/043—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of metal
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C15/00—Surface treatment of glass, not in the form of fibres or filaments, by etching
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
- C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
-
- 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
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- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Preparing Plates And Mask In Photomechanical Process (AREA)
- Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)
Abstract
The photomask blank has a substrate, and at least a1 st layer and a2 nd layer in this order from the substrate side, wherein the 1 st layer contains chromium, the 2 nd layer contains chromium and oxygen, and the arithmetic average height of the surface of the 2 nd layer is 0.245nm or more.
Description
Technical Field
The present invention relates to a photomask blank, a photomask, an exposure method, and a device manufacturing method.
Background
A photomask blank is known in which a light-shielding layer made of a chromium-containing material and a reflection reducing layer made of a laminated film made of a plurality of layers made of a chromium oxide material are laminated on a transparent substrate (patent document 1).
Prior art literature
Patent literature
Patent document 1: japanese patent laid-open publication 2016-105158
Disclosure of Invention
According to the 1 st aspect of the present invention, a photomask blank comprises a substrate, and at least a1 st layer and a2 nd layer in this order from the substrate side, wherein the 1 st layer contains chromium, the 2 nd layer contains chromium and oxygen, and the arithmetic average height of the surface of the 2 nd layer is 0.245nm or more.
According to claim 2 of the present invention, the photomask blank has a substrate, and at least a1 st layer and a2 nd layer are provided in this order from the substrate side, the 1 st layer contains chromium, the 2 nd layer contains chromium and oxygen, and a difference between an arithmetic average height of a surface of the 2 nd layer and an arithmetic average height of a surface of the substrate is 0.03nm or more.
According to claim 3 of the present invention, the photomask is formed by forming the 1 st layer and the 2 nd layer of the photomask blank of claim 1 or 2 in a predetermined pattern.
According to the 4 th aspect of the present invention, the exposure method exposes the photosensitive substrate coated with the photoresist through the photomask according to the 3 rd aspect.
According to the 5 th aspect of the present invention, a method for manufacturing a device includes: an exposure step of exposing the photosensitive substrate by the exposure method according to the 4 th aspect; and a developing step of developing the exposed photosensitive substrate.
Drawings
Fig. 1 is a diagram showing a configuration example of a photomask blank according to an embodiment.
Fig. 2 is a schematic diagram showing an example of a manufacturing apparatus that can be used for manufacturing a photomask blank.
Fig. 3 is a table showing measurement results of photomask blanks of examples and comparative examples.
Fig. 4 is a schematic diagram showing a cross-sectional shape of a mask pattern produced using the photomask blank of the embodiment.
Fig. 5 is a schematic view showing a case where a photosensitive substrate is exposed through a photomask.
Fig. 6 is a diagram showing a configuration example of a photomask blank of a comparative example.
Fig. 7 is a schematic diagram showing a cross-sectional shape of a mask pattern produced using a photomask blank of a comparative example.
Detailed Description
(embodiment)
Fig. 1 is a diagram showing an example of the structure of a photomask blank 10 according to the present embodiment. The photomask blank 10 is provided with a substrate 11, a1 st layer (hereinafter referred to as a light-shielding layer) 12, and a2 nd layer (hereinafter referred to as a low reflection layer) 13. In the photomask blank 10 of the present embodiment, as shown in fig. 1, fine irregularities (a predetermined arithmetic average height) are provided on the surface of the low reflection layer 13 at a predetermined level. In the present embodiment, the oxygen content (atomic number concentration of oxygen) of the low reflection layer 13 is adjusted by sputtering, whereby a predetermined arithmetic average height is generated on the surface of the low reflection layer 13. The present embodiment will be described in detail below.
The substrate 11 is made of synthetic quartz glass or the like. The material of the substrate 11 may be any material that allows exposure light used in the exposure step in the device manufacturing process to pass therethrough. The light shielding layer 12 is made of a material containing chromium (Cr), and is formed on the substrate 11. The light shielding layer 12 is, for example, a CrCN film as a chromium-based material containing chromium, carbon (C), and nitrogen (N). The light shielding layer 12 has a function of shielding exposure light used in the exposure process. The light shielding layer 12 may be formed of a single film or may be formed by stacking 2 or more films.
The low reflection layer 13 is a CrOCN film as a material containing chromium and oxygen (O), for example, a chromium-based material containing chromium, oxygen, carbon, and nitrogen, and is laminated on the light shielding layer 12. When a photomask is produced using the photomask blank 10, a photoresist is coated on the surface of the low reflection layer 13 (the surface opposite to the surface contacting the light-shielding layer 12). The low reflection layer 13 has the following functions: when a desired pattern is drawn on the formed photoresist layer by the exposure light, reflection of the exposure light is reduced (suppressed). This prevents the reduction of the shape accuracy of the drawn pattern due to the reflection of the exposure light. When the device substrate is exposed through the photomask having the light-shielding layer 12 and the low reflection layer 13 formed in the desired pattern, the photomask is used with the surface on which the desired pattern is formed being the lower surface (the light-emitting side surface of the exposure light). At this time, exposure light reaching the device substrate through the photomask may be reflected toward the photomask. When the reflected exposure light further reflects from the surface of the photomask and reaches the device substrate, the exposure light is irradiated to the device substrate other than the region to be irradiated with the exposure light, which results in poor exposure. However, in the present embodiment, since the low reflection layer 13 is formed, reflection of exposure light on the photomask surface is reduced, and the exposure light passing through the low reflection layer 13 is absorbed in the light shielding layer 12, so that the above-described exposure failure can be suppressed. The low reflection layer 13 may be formed of a single film or may be formed by stacking 2 or more films.
The photomask blank 10 is suitable for use as a photomask blank for manufacturing a display device such as an FPD (Flat panel Display ) or a semiconductor device such as an LSI (Large Scale Integration, large-scale integrated circuit), for example. To manufacture a photomask using photomask blank 10, for example, the steps described below are performed.
A pattern is drawn on the photoresist layer formed on the low reflection layer 13 of the photomask blank 10 by energy rays such as laser light, electron beam, or ion beam. By developing the patterned photoresist layer, the patterned or non-patterned portion is removed, and a pattern is formed in the photoresist layer. Next, wet etching is performed using the formed pattern as a mask, whereby a shape corresponding to the pattern formed in the photoresist layer is formed in the low reflection layer 13 and the light shielding layer 12. Finally, the photoresist layer of the portion functioning as a mask is removed, thereby completing the photomask.
The inventors examined the relationship between the arithmetic average height of the low reflection layer 13 and the peeling of the interface between the low reflection layer 13 and the photoresist layer when the photoresist layer formed on the surface of the low reflection layer 13 was patterned by wet etching. The result shows that: when the surface of the low reflection layer 13 is set to a predetermined arithmetic average height, peeling of the interface between the low reflection layer 13 and the photoresist layer can be suppressed. The arithmetic average height in this specification refers to a value specified in ISO 25178. The reason why the peeling of the low reflection layer 13 and the photoresist layer at the interface therebetween can be suppressed is presumably because: by setting the surface of the low reflection layer 13 to a predetermined arithmetic average height, adhesion between the low reflection layer 13 and the photoresist layer is improved.
As described later, it can be seen that: when the arithmetic average height of the surface of the low reflection layer 13 is 0.245nm or more, the adhesion between the low reflection layer 13 and the photoresist layer is high, and the photomask blank 10 satisfying such a condition can effectively prevent the etching liquid from penetrating into the interface between the low reflection layer 13 and the photoresist layer during wet etching.
In order to set the surface of the low reflection layer 13 to a predetermined arithmetic average height, for example, when the low reflection layer 13 is formed by sputtering, the flow rate of oxygen introduced into the sputtering chamber is adjusted so that the low reflection layer 13 contains a predetermined amount or more of oxygen.
An example of a method for manufacturing photomask blank 10 according to the present embodiment will be described below.
Fig. 2 is a schematic diagram showing an example of a manufacturing apparatus used for manufacturing the photomask blank 10 according to the present embodiment. Fig. 2 (a) is a schematic view of the inside of the manufacturing apparatus 100 when the manufacturing apparatus 100 is viewed from the top surface, and fig. 2 (b) is a schematic view of the inside of the manufacturing apparatus 100 when the manufacturing apparatus is viewed from the side. The manufacturing apparatus 100 shown In fig. 2 is an In-Line (In-Line) sputtering apparatus, and includes: a chamber 20 for carrying in a substrate 11 for producing a photomask blank 10; a1 st sputtering chamber 21; a buffer chamber 22; a2 nd sputtering chamber 23; and a chamber 24 for carrying out the produced photomask blank 10.
The substrate tray 30 is a frame-shaped tray on which the substrate 11 for manufacturing the photomask blank 10 can be placed, and supports and places the outer edge portion of the substrate 11. The substrate 11 is placed on the substrate tray 30 such that the surface is polished and cleaned, and the surfaces on which the light shielding layer 12 and the low reflection layer 13 are formed are on the lower side (downward). In the sputtering apparatus 100, as described later, while maintaining a state in which the surface of the substrate 11 is opposed to the target, the substrate tray 30 on which the substrate 11 is mounted is moved in a direction indicated by a broken-line arrow 25 in fig. 2, and the light shielding layer 12 and the low reflection layer 13 are formed on the surface of the substrate 11.
The carry-in chamber 20, the 1 st sputtering chamber 21, the buffer chamber 22, the 2 nd sputtering chamber 23, and the carry-out chamber 24 are each partitioned by a partition plate, not shown. The carry-in chamber 20, the 1 st sputtering chamber 21, the buffer chamber 22, the 2 nd sputtering chamber 23, and the carry-out chamber 24 are connected to an exhaust device, not shown, respectively, and the inside of each chamber is exhausted.
The 1 st target 41 is provided in the 1 st sputtering chamber 21, and the 2 nd target 42 is provided in the 2 nd sputtering chamber 23. DC power supplies, not shown, are provided in each of the 1 st sputtering chamber 21 and the 2 nd sputtering chamber 23, and power is supplied to each of the 1 st target 41 and the 2 nd target 42.
The 1 st sputtering chamber 21 is provided with a1 st gas inlet 31 for introducing a sputtering gas into the 1 st sputtering chamber 21. The 1 st target 41 is a sputtering target for forming the light shielding layer 12, and is formed of a material containing chromium. Specifically, the 1 st target 41 is formed of a material selected from chromium, chromium oxide, chromium nitride, chromium carbide, and the like. For example, in order to form a CrCN film as the light shielding layer 12, a mixed gas of a gas containing nitrogen and carbon and an inert gas (argon gas or the like) is introduced through the 1 st gas inlet 31.
The 2 nd sputtering chamber 23 is provided with a2 nd gas inlet 32 for introducing a sputtering gas into the 2 nd sputtering chamber 23. The 2 nd target 42 is a sputtering target for forming the low reflection layer 13, and is formed of a material containing chromium (chromium or the like). For example, in order to form a CrOCN film as the low reflection layer 13, a mixed gas of a gas containing oxygen, nitrogen, and carbon and an inert gas is introduced through the 2 nd gas inlet 32.
When the substrate 11 is transferred to the 1 st sputtering chamber 21, a light shielding layer 12 (CrCN film) is formed on the surface of the substrate 11 by sputtering in the 1 st sputtering chamber 21. The substrate 11 on which the light shielding layer 12 is formed is transferred to the 2 nd sputtering chamber 23 via the buffer chamber 22. In the 2 nd sputtering chamber 23, the low reflection layer 13 (CrOCN film) is formed on the surface of the light shielding layer 12 by sputtering. The substrate 11 formed with the light shielding layer 12 and the low reflection layer 13 is transferred to the carry-out chamber 24. In this way, the light shielding layer 12 and the low reflection layer 13 are sequentially formed on the surface of the substrate 11, and the photomask blank 10 is manufactured.
The materials of the 1 st and 2 nd targets 41 and 42 and the types of the gases introduced from the 1 st and 2 nd gas inlets 31 and 32 are appropriately selected according to the materials or compositions constituting the light shielding layer 12 or the low reflection layer 13. The sputtering method may be any method such as DC sputtering, RF sputtering, or ion beam sputtering.
As described above, in the present embodiment, in order to set the surface of the low reflection layer 13 to a predetermined arithmetic average height, when the low reflection layer 13 is formed by sputtering, the amount of oxygen contained in the sputtering gas introduced into the 2 nd sputtering chamber 23 is adjusted so that the low reflection layer 13 contains a predetermined amount or more of oxygen. Thereby, the arithmetic average height of the low reflection layer 13 is adjusted. By setting the surface of the low reflection layer 13 to a predetermined arithmetic average height, adhesion between the low reflection layer 13 and the photoresist is improved, and thus, the etching liquid can be prevented from penetrating into the interface between the low reflection layer 13 and the photoresist when wet etching is performed on the photomask blank 10. As a result, when a photomask is manufactured using the photomask blank 10 of the present embodiment, a pattern can be formed with good accuracy. Therefore, the yield of the photomask manufacturing process can be improved.
In addition, by performing an exposure process using a photomask manufactured from the photomask blank 10 of the present embodiment, a high-definition device can be manufactured. In addition, occurrence of defects in the circuit pattern during the exposure process can be reduced, and the yield of the device manufacturing process can be improved.
According to the above embodiment, the following operational effects are obtained.
(1) The photomask blank 10 is a photomask blank 10 having a substrate 11 and having at least a light-shielding layer 12 and a low reflection layer 13 in this order from the substrate side. The light shielding layer 12 contains chromium, the low reflection layer 13 contains chromium and oxygen, and the arithmetic average height of the surface of the low reflection layer 13 is 0.245nm or more. When the arithmetic average height of the surface of the low reflection layer 13 is 0.245nm or more, the adhesion between the low reflection layer 13 and the photoresist layer is improved. This can suppress the phenomenon that the etching liquid penetrates into the interface between the low reflection layer 13 and the photoresist layer during wet etching.
(2) When a photomask is manufactured using the photomask blank 10 of the present embodiment, a pattern can be formed with good accuracy. Therefore, the yield of the photomask manufacturing process can be improved. In addition, the formation of the inclined surface due to the etching liquid penetrating into the low reflection layer 13 or the light shielding layer 12 at the pattern edge portion can be prevented, and the reduction of the function of reducing the reflection of the low reflection layer 13 and the reduction of the light shielding function by the light shielding layer 12 can be caused.
Example 1
First, a transparent glass substrate 11 made of synthetic quartz glass is prepared. A light shielding layer 12 and a low reflection layer 13 are sequentially formed on the surface of the glass substrate 11 using the in-line sputtering apparatus 100 shown in fig. 2. Hereinafter, a method for manufacturing each of the light shielding layer 12 and the low reflection layer 13 will be described in more detail.
Argon (Ar), nitrogen (N) 2 ) And methane (CH) 4 ) Is mixed with Ar, N 2 、CH 4 The flow rates of the respective gases were set to 172.8sccm, 60sccm, 7.2sccm, and the pressure was set to 0.6 Pa), and the gases were introduced into the 1 st sputtering chamber 21. While sputtering gas was introduced, sputtering was performed by setting the power of the DC power supply of the 1 st sputtering chamber 21 to 8.5kW, and the light shielding layer 12 made of CrCN was formed on the substrate 11 at a thickness of 70 nm.
Then, argon (Ar) and carbon dioxide (CO 2 ) Nitrogen (N) 2 ) And oxygen (O) 2 ) Is mixed with Ar and CO 2 、N 2 、O 2 The flow rates of the respective gases were set to 240sccm, 45sccm, 120sccm, 6sccm, and the pressure was 0.3 Pa), respectively, as sputtering gases, and were introduced into the 2 nd sputtering chamber 23. The sputtering was performed by setting the power of the DC power supply of the 2 nd sputtering chamber 23 to 8.5kW, and the low reflection layer 13 made of CrOCN was formed on the surface of the light shielding layer 12 at a thickness of 30 nm.
The arithmetic average height Sa of the surface of the low reflection layer 13 in the range of 86.9 μm×86.9 μm was measured by a coherent scanning interferometer (NewView 8000 manufactured by Zygo corporation) in the photomask blank 10 manufactured by the above-described steps. The atomic number concentration of oxygen in the depth direction of the low reflection layer 13 was measured by an X-ray photoelectron spectroscopy device (QuanteraII manufactured by PHI corporation). These measurement results are shown in the table of fig. 3.
After the produced photomask blank 10 was subjected to UV cleaning for 10 minutes, spin cleaning (megasonic cleaning, alkali cleaning, brush cleaning, rinsing, spin drying) was performed for 15 minutes, and a photoresist layer was formed on the surface of the low reflection layer 13 by a spin coater. Next, the resist pattern was formed by exposing the resist pattern to light with a line space ratio of 2 μm using a mask aligner, followed by development to remove the photoresist layer portion. The resist pattern is used as a mask, and the photomask blank 10 having the resist pattern formed thereon is immersed in an etching solution based on ceric ammonium nitrate to be wet-etched, whereby a pattern is formed in the low reflection layer 13 and the light shielding layer 12.
After the pattern was formed, the pattern was cut off, and the cross-sectional shape of the pattern was observed by a Scanning Electron Microscope (SEM), and it was confirmed from the cross-sectional shape of the pattern whether or not the penetration of the etching solution occurred at the interface portion between the photoresist layer and the low reflection layer 13. The results are shown in the table of fig. 3.
Example 2
A substrate 11 made of synthetic quartz glass was prepared as in the substrate 11 used in example 1. The light shielding layer 12 was formed under the same conditions as in example 1. Next, in example 1, oxygen (O) introduced into the 2 nd sputtering chamber 23 was introduced when the low reflection layer 13 was formed 2 ) The flow rate of (C) was set to 6sccm, but in this example, oxygen (O) 2 ) Except that the flow rate of (a) was 18sccm, the low reflection layer 13 was formed under the same conditions as in example 1. The same items as in example 1 were measured. The measurement results are shown in the table of fig. 3.
Example 3
A substrate 11 made of synthetic quartz glass was prepared as in the substrate 11 used in example 1. The light shielding layer 12 was formed under the same conditions as in example 1. Next, when the low reflection layer 13 is formed, oxygen (O) introduced into the 2 nd sputtering chamber 23 2 ) The flow rate of (2) was set to 30sccm. The low reflection layer 13 was formed under the same conditions as in example 1 except for the flow rate of oxygen. The same items as in example 1 were measured. The measurement results are shown in the table of fig. 3.
Example 4
A substrate 11 made of synthetic quartz glass was prepared as in the substrate 11 used in example 1. The light shielding layer 12 was formed under the same conditions as in example 1. Next, when the low reflection layer 13 is formed, oxygen (O) introduced into the 2 nd sputtering chamber 23 2 ) Except that the flow rate of (a) was 48sccm, the low reflection layer 13 was formed under the same conditions as in example 1. The same items as in example 1 were measured. The measurement results are shown in the table of fig. 3.
Comparative example 1
A substrate 51 made of synthetic quartz glass was prepared as in the substrate 11 used in example 1. The light shielding layer 52 was formed under the same conditions as in example 1. Next, when the low reflection layer 53 is formed, oxygen (O) introduced into the 2 nd sputtering chamber 23 2 ) Except that the amount of (a) was 0sccm, the low reflection layer 53 was formed under the same conditions as in example 1. That is, in comparative example 1, oxygen was not introduced into the 2 nd sputtering chamber 23 at the time of forming the low reflection layer 53. Fig. 6 is a schematic diagram showing the structure of a photomask blank 50 produced, in which a light-shielding layer 52 and a low-reflection layer 53 are sequentially formed on the surface of a substrate 51 in the photomask blank 50 of comparative example 1. In addition, the same items as in example 1 were measured. The measurement results are shown in the table of fig. 3.
In the table shown in fig. 3, regarding example 1, example 2, example 3, example 4, and comparative example 1, the oxygen atom number concentration in the vicinity of the surface of the low reflection layer (surface layer), the oxygen atom number concentration at a position of 5nm deep from the surface of the low reflection layer, the arithmetic average height Sa1 of the surface of the low reflection layer, the difference between the arithmetic average height Sa1 of the low reflection layer and the arithmetic average height Sa2 of the substrate (the value obtained by subtracting the value of Sa2 from the value of Sa 1), and the presence or absence of etching liquid infiltration are shown. As is clear from fig. 3, the arithmetic average height of the low reflection layer surfaces in examples 1 to 4 was larger than 0.245nm, whereas the arithmetic average height of the low reflection layer surfaces in comparative example 1 was 0.242nm, which is smaller than examples 1 to 4. In addition, from the surface depth 5nm position (from the surface position) of oxygen atom number concentration than the surface near (surface layer) oxygen atom number concentration.
Fig. 4 is a view schematically showing a case where the photomask blank 10 manufactured in examples 1 to 4 was wet etched, then cut off, and the cross section of the pattern was observed by a Scanning Electron Microscope (SEM). In the photomask blank 10, a pattern corresponding to a mask formed on the photoresist layer 15 is formed on the low reflection layer 13 and the light shielding layer 12 by wet etching. As shown in fig. 4, it is confirmed that: the photomask blanks 10 manufactured in examples 1 to 4 were not observed with inclined surfaces due to penetration of the etching liquid at the edge portions of the patterns after wet etching, and the edge portions of the patterns were constituted by substantially perpendicular surfaces to the substrate 11. That is, in examples 1 to 4, when the low reflection layer 13 was formed by sputtering, the flow rate of oxygen introduced into the sputtering chamber was adjusted so that the surface of the low reflection layer 13 had a predetermined arithmetic average height. This is considered to improve adhesion between the photoresist and the low reflection layer 13.
Fig. 7 is a view schematically showing a case where the photomask blank 50 manufactured in comparative example 1 was wet etched, then cut off, and a pattern cross section was observed by a Scanning Electron Microscope (SEM). As shown in fig. 7, the photomask blank 50 produced in comparative example 1 was wet etched, and then inclined surfaces due to the penetration of the etching liquid were observed at the boundary between the photoresist layer 55 and the low reflection layer 53 at the edge portion of the pattern.
In the photomask in which such an inclined surface is formed, the thickness of the low reflection layer is reduced in the region in which the inclined surface is formed, and thus the function of reducing reflection of exposure light is reduced. As a result, when a circuit pattern is formed on the device substrate using such a photomask, the accuracy of the circuit pattern formed on the device substrate is lowered. When the penetration of the etching liquid is larger, a large inclined surface is formed so as to cross the low reflection layer and the light shielding layer. In such a photomask, in addition to the reduction of the function of reducing the reflection of the exposure light by the low reflection layer, the light shielding performance of the exposure light by the light shielding layer is also reduced. Therefore, such photomasks are not suitable for device fabrication.
From the above results, when oxygen is introduced into the sputtering chamber at the time of forming the low reflection layer 13, the value represented by the arithmetic average height Sa1 of the surface of the low reflection layer becomes large, and the adhesion between the photoresist layer and the low reflection layer 13 can be made to be a sufficient level by setting the arithmetic average height Sa1 to a predetermined level. When the arithmetic average height Sa1 of the surface of the low reflection layer 13 is 0.245nm or more, the adhesion between the photoresist layer and the low reflection layer 13 is sufficiently large, and it is considered that the etching solution can be prevented from penetrating into the interface between them. The value of the arithmetic mean height Sa1 of the surface of the low reflection layer 13 is not particularly limited as long as the desired antireflection performance is obtained, and the upper limit value may be, for example, 1.0nm.
Based on the measurement results of fig. 3, the low reflection layer 13 preferably has an oxygen atom number concentration of 44% or more at the surface layer. The low reflection layer 13 preferably has an oxygen atom number concentration of 35% or more at a depth of 5nm from the surface. This can improve the adhesion between the photoresist layer and the low reflection layer 13, and can prevent the etching liquid from penetrating into the interface between them.
In addition, the surface of the substrate 11 of the photomask blank 10 is generally polished by grinding. In contrast, since the low reflection layer 13 is formed by sputtering, the arithmetic average height of the substrate 11 is smaller in the short period component than the arithmetic average height of the low reflection layer 13. Further, it is considered that the short period component of the arithmetic average height of the low reflection layer 13 acts more effectively on the adhesion with the photoresist, not the substrate 11 but the low reflection layer 13, which is in direct contact with the photoresist. Therefore, the difference between the arithmetic average height Sa1 of the surface of the low reflection layer 13 and the arithmetic average height Sa2 (0.217 nm in the present embodiment and comparative example) of the surface of the substrate 11 is preferably 0.03nm or more. In addition, from the aspect of pattern edge roughness after etching, the upper limit value of the difference between the arithmetic average height Sa1 of the surface of the low reflection layer 13 and the arithmetic average height Sa2 of the surface of the substrate 11 may be set to 1.0nm.
The following modifications are also within the scope of the present invention, and one or two or more of the modifications may be combined with the above-described embodiments.
Modification 1
In the above embodiment, when the low reflection layer 13 is formed by sputtering, the flow rate of oxygen introduced into the sputtering chamber is adjusted so that the arithmetic average height of the low reflection layer 13 is within a predetermined range. However, instead of adjusting the flow rate of oxygen introduced into the sputtering chamber, or in addition to this, the surface of the low reflection layer 13 may be formed to have a predetermined arithmetic average height by dry etching or wet etching. This can improve adhesion between the photoresist and the low reflection layer 13.
The photomask blank 10 described in the above embodiment and modification can be suitably used as a photomask blank for manufacturing a photomask for manufacturing a display device, for manufacturing a semiconductor, or for manufacturing a printed circuit board. In the case of a photomask blank used for manufacturing a photomask for manufacturing a display device, a substrate having dimensions of 520mm×800mm or more may be used as the substrate 11. The thickness of the substrate 11 may be 8mm to 21mm.
Next, as an application example of a photomask manufactured by using the photomask blank 10 manufactured in examples 1 to 4, a photolithography process for manufacturing a semiconductor or a liquid crystal panel will be described with reference to fig. 5. In the exposure apparatus 500, a photomask 513 manufactured using the photomask blank 10 manufactured in examples 1 to 4 was used. In addition, a photosensitive substrate 515 coated with a photoresist is also disposed in the exposure apparatus 500.
The exposure apparatus 500 includes: a light source LS; an illumination optical system 502; a mask support table 503 holding a photomask 513; a projection optical system 504; an exposure object support 505 for holding a photosensitive substrate 515 as an exposure object; and a driving mechanism 506 for moving the exposure object support 505 in the horizontal plane. The exposure light emitted from the light source LS of the exposure apparatus 500 is incident on the illumination optical system 502, adjusted to a predetermined beam, and irradiated onto the photomask 513 held by the mask support table 503. The light passing through the photomask 513 has an image of the device pattern drawn by the photomask 513, and the light is irradiated to a predetermined position of the photosensitive substrate 515 held by the exposure object support 505 through the projection optical system 504. Thus, the image of the device pattern of the photomask 513 is imagewise exposed to the photosensitive substrate 515 such as a semiconductor wafer or a liquid crystal panel at a predetermined magnification.
While various embodiments and modifications have been described above, the present invention is not limited to these. Other modes conceivable within the scope of the technical idea of the present invention are also included in the scope of the present invention.
The disclosures of the following priority base applications are incorporated by reference into this invention.
Japanese patent application 2017 No. 171997 (submitted on 2017, 9 and 7 days)
Symbol description
10 … photomask blank, 11 … substrate, 12 … light shielding layer, 13 … low reflection layer, and 100 … manufacturing apparatus
Claims (14)
1. A photomask blank having a substrate and having at least a light-shielding layer and a low reflection layer in this order from the substrate side,
the light-shielding layer contains chromium and,
the low reflection layer contains chromium and oxygen,
the arithmetic average height of the surface of the low reflection layer is 0.245nm or more as prescribed in ISO 25178.
2. The photomask blank according to claim 1, wherein a difference between an arithmetic average height of a surface of the low-reflection layer specified according to ISO25178 and an arithmetic average height of a surface of the substrate specified according to ISO25178 is 0.03nm or more.
3. The photomask blank of claim 1 or 2, wherein the low-reflection layer is contiguous with the light-shielding layer.
4. The photomask blank of claim 1 or 2, wherein the low-reflection layer is CrOCN or a layer with more oxygen than stoichiometric in CrOCN.
5. The photomask blank according to claim 1 or 2, wherein the concentration of oxygen atoms in the surface layer of the low-reflection layer is 44% or more.
6. The photomask blank of claim 5, wherein the concentration of oxygen atoms in the surface layer of the low-reflection layer is a value measured using an X-ray photoelectron spectroscopy device.
7. The photomask blank according to claim 1 or 2, wherein the low-reflection layer has an oxygen atom number concentration of 35% or more at a depth of 5nm from the surface.
8. The photomask blank of claim 7, wherein the concentration of oxygen atoms in the low-reflection layer at a depth of 5nm from the surface is a value measured using an X-ray photoelectron spectroscopy device.
9. The photomask blank according to claim 1 or 2, wherein the surface of the low reflection layer is wet etched or dry etched.
10. The photomask blank according to claim 1 or 2, wherein the substrate is rectangular, and the size of the substrate is 520mm x 800mm or more.
11. The photomask blank according to claim 1 or 2, wherein the substrate is composed of quartz glass.
12. A photomask in which the light shielding layer and the low reflection layer of the photomask blank according to any one of claims 1 to 11 are formed in a predetermined pattern.
13. An exposure method for exposing a photosensitive substrate coated with a photoresist through the photomask of claim 12.
14. A method of manufacturing a device, comprising:
an exposure step of exposing the photosensitive substrate by the exposure method according to claim 13; and a developing step of developing the photosensitive substrate after exposure.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2017171997 | 2017-09-07 | ||
| JP2017-171997 | 2017-09-07 | ||
| PCT/JP2018/032984 WO2019049919A1 (en) | 2017-09-07 | 2018-09-06 | Photomask blank, photomask, light exposure method and method for producing device |
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| CN110809735A CN110809735A (en) | 2020-02-18 |
| CN110809735B true CN110809735B (en) | 2023-04-21 |
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| JP (1) | JP7167922B2 (en) |
| KR (1) | KR102631490B1 (en) |
| CN (1) | CN110809735B (en) |
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| KR20240043366A (en) * | 2022-09-27 | 2024-04-03 | 엘지이노텍 주식회사 | Metal substrate and mask comprising the same |
| KR102745061B1 (en) * | 2024-01-11 | 2024-12-23 | (주)네프코 | Tranparent photomask with easily detaching for contact lithography process and Manufacturing method of the Same |
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| JP2006146152A (en) * | 2004-10-22 | 2006-06-08 | Shin Etsu Chem Co Ltd | Photomask blank, photomask, and manufacturing method thereof |
| JP2007233179A (en) * | 2006-03-02 | 2007-09-13 | Shin Etsu Chem Co Ltd | Photomask blank and photomask |
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| JP4088742B2 (en) * | 2000-12-26 | 2008-05-21 | 信越化学工業株式会社 | Photomask blank, photomask, and method for manufacturing photomask blank |
| JP3956103B2 (en) * | 2002-02-26 | 2007-08-08 | 信越化学工業株式会社 | Photomask blank, photomask and photomask blank evaluation method |
| JP4509050B2 (en) * | 2006-03-10 | 2010-07-21 | 信越化学工業株式会社 | Photomask blank and photomask |
| JP4668881B2 (en) * | 2006-10-10 | 2011-04-13 | 信越石英株式会社 | Surface treatment method for quartz glass substrate and hydrogen radical etching apparatus |
| US8404406B2 (en) * | 2008-03-31 | 2013-03-26 | Hoya Corporation | Photomask blank and method for manufacturing the same |
| TW200949430A (en) * | 2008-03-31 | 2009-12-01 | Hoya Corp | Photo mask blank and manufacturing method thereof |
| US8304147B2 (en) * | 2008-03-31 | 2012-11-06 | Hoya Corporation | Photomask blank, photomask, and method for manufacturing photomask blank |
| KR102228638B1 (en) * | 2013-01-18 | 2021-03-16 | 호야 가부시키가이샤 | Method for manufacturing mask blank substrate, method for manufacturing mask blank and method for manufacturing transfer mask |
| SG11201508901XA (en) * | 2013-09-18 | 2015-11-27 | Hoya Corp | Reflective mask blank and method for manufacturing same, reflective mask, and method for manufacturing semiconductor device |
| JP2016057577A (en) * | 2014-09-12 | 2016-04-21 | 信越化学工業株式会社 | Photomask blank |
| JP2016057578A (en) * | 2014-09-12 | 2016-04-21 | 信越化学工業株式会社 | Photomask blank |
| JP6594742B2 (en) * | 2014-11-20 | 2019-10-23 | Ｈｏｙａ株式会社 | Photomask blank, photomask manufacturing method using the same, and display device manufacturing method |
| JP6375269B2 (en) * | 2015-07-01 | 2018-08-15 | 信越化学工業株式会社 | INORGANIC MATERIAL FILM, PHOTOMASK BLANK, AND PHOTOMASK MANUFACTURING METHOD |
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- 2018-09-06 WO PCT/JP2018/032984 patent/WO2019049919A1/en active Application Filing
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2006146152A (en) * | 2004-10-22 | 2006-06-08 | Shin Etsu Chem Co Ltd | Photomask blank, photomask, and manufacturing method thereof |
| JP2007233179A (en) * | 2006-03-02 | 2007-09-13 | Shin Etsu Chem Co Ltd | Photomask blank and photomask |
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| JPWO2019049919A1 (en) | 2020-10-15 |
| JP7167922B2 (en) | 2022-11-09 |
| TWI774840B (en) | 2022-08-21 |
| TW201922489A (en) | 2019-06-16 |
| WO2019049919A1 (en) | 2019-03-14 |
| KR102631490B1 (en) | 2024-01-30 |
| CN110809735A (en) | 2020-02-18 |
| KR20200044784A (en) | 2020-04-29 |
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