WO2020017270A1 - Procédé de fabrication de masque métallique et masque métallique, et procédé de fabrication de réseau de diffraction à rapport d'aspect élevé et réseau de diffraction à rapport d'aspect élevé - Google Patents

Procédé de fabrication de masque métallique et masque métallique, et procédé de fabrication de réseau de diffraction à rapport d'aspect élevé et réseau de diffraction à rapport d'aspect élevé Download PDF

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Publication number
WO2020017270A1
WO2020017270A1 PCT/JP2019/025524 JP2019025524W WO2020017270A1 WO 2020017270 A1 WO2020017270 A1 WO 2020017270A1 JP 2019025524 W JP2019025524 W JP 2019025524W WO 2020017270 A1 WO2020017270 A1 WO 2020017270A1
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Prior art keywords
metal mask
diffraction grating
etching
aspect ratio
silicon substrate
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PCT/JP2019/025524
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English (en)
Japanese (ja)
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一成 多田
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コニカミノルタ株式会社
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Publication of WO2020017270A1 publication Critical patent/WO2020017270A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/04—Coating on selected surface areas, e.g. using masks
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D1/00—Electroforming
    • C25D1/08—Perforated or foraminous objects, e.g. sieves
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/18—Diffraction gratings
    • G—PHYSICS
    • G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
    • G21K—TECHNIQUES FOR HANDLING PARTICLES OR IONISING RADIATION NOT OTHERWISE PROVIDED FOR; IRRADIATION DEVICES; GAMMA RAY OR X-RAY MICROSCOPES
    • G21K1/00—Arrangements for handling particles or ionising radiation, e.g. focusing or moderating
    • G21K1/06—Arrangements for handling particles or ionising radiation, e.g. focusing or moderating using diffraction, refraction or reflection, e.g. monochromators
    • 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
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
    • H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
    • H01L21/3065—Plasma etching; Reactive-ion etching

Definitions

  • the present invention relates to a method for manufacturing a metal mask used for manufacturing a diffraction grating or the like, a metal mask, a method for manufacturing a high aspect ratio diffraction grating which can be suitably used for a Talbot interferometer or a Talbot-Lau interferometer, and a high aspect ratio.
  • a diffraction grating is related to a method for manufacturing a metal mask used for manufacturing a diffraction grating or the like, a metal mask, a method for manufacturing a high aspect ratio diffraction grating which can be suitably used for a Talbot interferometer or a Talbot-Lau interferometer, and a high aspect ratio.
  • a diffraction grating is related to a diffraction grating.
  • Diffraction gratings are used as spectroscopic elements having a large number of parallel periodic structures in optical systems of various devices, and in recent years, applications to X-ray imaging devices have been attempted. Diffraction gratings are classified according to diffraction methods into transmission diffraction gratings and reflection diffraction gratings. Furthermore, a transmission type diffraction grating is an amplitude type diffraction grating (absorption type diffraction grating) in which light absorbing portions are periodically arranged on a substrate that transmits light, and a phase of light is changed on a substrate that transmits light. A phase type diffraction grating in which portions to be formed are periodically arranged is exemplified.
  • X-rays used in an X-ray imaging apparatus generally have very small absorption by a substance and a small phase change.
  • a diffraction grating for X-rays is manufactured from gold (Au) having a relatively large X-ray absorption capacity
  • the thickness of the gold is required to be about 100 ⁇ m, and the transmission portion and the portion where the absorption or phase changes are equal in width.
  • the ratio of the thickness to the width of the gold portion is a high aspect ratio of 5 or more. It is technically difficult to stably manufacture such a structure having a high aspect ratio.
  • a method for manufacturing a diffraction grating having such a high aspect ratio structure is disclosed in, for example, JP-A-2009-037023.
  • the method of manufacturing a diffraction grating disclosed in the above-mentioned patent document is a method of manufacturing a diffraction grating used for an X-ray Talbot interferometer.
  • the X-ray absorbing metal part is formed to a required thickness. Many steps were required, there was a problem in productivity, and the aspect ratio was low, and the performance as a diffraction grating was insufficient.
  • a G0 diffraction grating (also referred to as a source diffraction grating or a multi-slit) applied to a current diffraction grating for X-ray Talbot plays a role of generating coherent X-rays having interference capability, and has an S / N ratio of an image.
  • This G0 diffraction grating forms an X-ray blocking portion by filling a silicon substrate that transmits X-rays and a concave portion (slit portion) of the concavo-convex structure formed on the silicon substrate with a metal component, for example, gold. .
  • the contrast is obtained by recording the intensity of the X-ray transmitted through the imaging target as it is.
  • the voltage is increased, X in a low aspect ratio concave portion formed by a metal component having a predetermined depth. Lines are transmitted, the coherence is reduced, and the S / N ratio is deteriorated, so that a clear image with high contrast cannot be obtained.
  • a diffraction grating using a metal grating having a high aspect ratio by utilizing the characteristics of silicon capable of forming a three-dimensional structure. That is, a slit groove having a periodic structure with a high aspect ratio is formed in a silicon substrate, and by utilizing the conductivity of silicon in the formed slit groove, a metal is buried by an electroplating method (electroforming method) to form a diffraction grating.
  • electroplating method electroplating method
  • Patent Document 1 there has been disclosed a method of forming a concave portion while etching using a mask, and forming a fine structure by repeating formation and etching of a protective film on the side surface of the formed concave portion (for example, Patent Reference 1).
  • Patent Document 1 when an attempt is made to produce a diffraction grating having a high-aspect-ratio concavo-convex structure in which the depth of a concave portion exceeds 300 ⁇ m, the mask becomes deeper as the depth becomes deeper.
  • the already formed lattice part directly below is damaged by etching during deep digging, and the shape of the tip is disturbed, so that a stable shape and a high aspect ratio irregular structure with a depth exceeding 300 ⁇ m can be formed. It was difficult.
  • the present invention has been made in view of the above problems, and a solution to the problem is mainly a method for manufacturing a metal mask that is suitable for manufacturing a diffraction grating having a high aspect ratio and has resistance during etching, and Using the obtained metal mask and the metal mask, for example, a method for producing a high-resolution high-aspect-ratio diffraction grating that can be suitably used for a Talbot interferometer or a Talbot-Lau interferometer and obtained by the method It is to provide a high aspect ratio diffraction grating.
  • the present inventor has conducted intensive studies in view of the above problems, and as a result, formed a lattice having a concavo-convex structure on the silicon substrate, filled an organic material into concave portions of the lattice and solidified to form an etching resist, and formed the etching resist.
  • a method for manufacturing a metal mask using a silicon substrate A first step of forming an aluminum layer on the silicon substrate; After applying a resist on the aluminum layer, patterning the resist, and then patterning the aluminum layer, a second step, A third step of etching the silicon substrate corresponding to the region from which the aluminum layer has been removed to form a lattice having an uneven structure; A fourth step of filling an organic material into the recesses of the lattice and solidifying to form an etching resist; A fifth step of removing the organic material by an etching method while leaving a bottom of the concave portion; A sixth step of applying metal plating to the upper surface and side surfaces from which the organic material has been removed; A seventh step of removing the organic material left on the bottom of the concave portion; A method for manufacturing a metal mask, comprising: manufacturing a metal mask through the method.
  • the silicon substrate having the concave-convex structure has a concave-convex structure in which a groove width is in a range of 1 to 50 ⁇ m and a depth of a concave groove is in a range of 1 to 150 ⁇ m.
  • a metal mask using a silicon substrate The silicon substrate has a lattice having an uneven structure, and A metal mask, wherein a metal plating is applied to side surfaces of the projections of the concavo-convex structure except an upper surface portion and a bottom portion.
  • a high aspect ratio diffraction grating using the metal mask according to item 4 A high aspect ratio diffraction grating, characterized in that the grating having an uneven structure has an uneven structure in which a metal plating is applied to a tip portion and a depth of a groove of the concave portion is in a range of 300 to 500 ⁇ m.
  • a method for manufacturing a metal mask suitable for manufacturing a diffraction grating having a high aspect ratio and having resistance during etching, and a metal mask obtained thereby, and using the metal mask for example, It is possible to provide a method for manufacturing a high-resolution high-aspect-ratio diffraction grating that can be suitably used for an interferometer or a Talbot-Lau interferometer, and a high-aspect-ratio diffraction grating obtained by the method.
  • a first step of forming an aluminum layer on the silicon substrate 1) applying a resist on the aluminum layer, patterning the resist, and then patterning the aluminum layer; 3) a third step of etching the silicon substrate corresponding to the region from which the aluminum layer has been removed to form a lattice having an uneven structure; 4) a fourth step of filling the recesses of the lattice with an organic material and solidifying to form an etching resist; 5) a fifth step of removing the organic material by an etching method while leaving the bottom of the concave portion; 6) a sixth step of applying metal plating to the upper surface and the side surfaces from which the organic material has been removed; 7) a seventh step of removing the organic material left on the bottom of the concave portion;
  • a diffraction grating having a stable shape without damage and having a high aspect ratio for example, a structure in which the depth of the concave portion exceeds 300 ⁇ m was obtained.
  • FIG. 2 is a schematic cross-sectional view showing an example of the entire configuration of a metal mask provided with metal plating of the present invention.
  • Schematic showing the first step of manufacturing a metal mask with metal plating Schematic view showing a second step of manufacturing a metal mask provided with metal plating
  • Schematic showing the third step of manufacturing a metal mask provided with metal plating Schematic showing a fourth step of manufacturing a metal mask with metal plating
  • Schematic showing a sixth step of manufacturing a metal mask with metal plating
  • Schematic showing an example of a method for forming a metal mask by electroforming Schematic view showing an example of a manufacturing process of a high aspect ratio diffraction grating using the metal mask of the present invention (metal mask preparation process)
  • FIG. 2 is a schematic cross-sectional view showing an example of the entire configuration of the high aspect ratio diffraction grating of the present invention.
  • 1 is a schematic perspective view showing an example of the entire configuration of a high aspect ratio diffraction grating of the present invention.
  • Conceptual diagram showing an example of a grating portion structure of a high aspect ratio diffraction grating of a comparative example The conceptual diagram which shows an example of the grating
  • Schematic configuration diagram showing an example of the configuration of an X-ray Talbot-Lau interferometer to which the high aspect ratio diffraction grating of the present invention is applied.
  • the method for manufacturing a metal mask of the present invention is a method for manufacturing a metal mask using a silicon substrate, 1) a first step of forming an aluminum layer on the silicon substrate; 2) applying a resist on the aluminum layer, patterning the resist, and then patterning the aluminum layer; 3) a third step of etching the silicon substrate corresponding to the region from which the aluminum layer has been removed to form a lattice having an uneven structure; 4) a fourth step of filling the recesses of the lattice with an organic material and solidifying to form an etching resist; 5) a fifth step of removing the organic material by an etching method while leaving the bottom of the concave portion; 6) a sixth step of applying metal plating to the upper surface and the side surfaces from which the organic material has been removed; 7) a seventh step of removing the organic material left on the bottom of the concave portion;
  • a metal mask is manufactured through the following. This feature is a technical feature common or corresponding to the invention according to each of the following embodiments.
  • the silicon substrate having the uneven structure has a groove width in the range of 1 to 50 ⁇ m and a depth of the groove of the concave portion. It is preferable to have a metal plated portion having a concavo-convex structure in the range of 1 to 150 ⁇ m in that a diffraction grating having a high aspect ratio can be stably manufactured.
  • an organic material as an etching resist formed by filling the concave portion of the metal mask can be easily removed by acetone or oxygen plasma treatment without damaging the silicon substrate constituting the lattice (convex portion). It is preferable in that it can be performed.
  • the method for manufacturing a high aspect ratio diffraction grating of the present invention uses the metal mask of the present invention, 1) an etching step of digging a concave portion of a silicon substrate of a metal mask having an uneven structure to a predetermined depth; 2) a step of forming an insulating layer on a surface portion and a concave portion surface of the silicon substrate which is deeply dug and having the uneven structure; 3) removing the insulating layer formed on the bottom of the concave portion; 4) an electroforming step of filling the recess with metal by electroforming; And producing a high aspect ratio diffraction grating.
  • a high aspect ratio diffraction grating of the present invention it is possible to form an X-ray blocking portion having a concave portion with a groove depth of 300 ⁇ m or more and made of a metal component having a sufficient thickness, preferably gold. And a high resolution, high aspect ratio diffraction grating can be obtained.
  • a portion where a lattice is formed is also referred to as a convex portion, a silicon layer or a lattice portion.
  • the recess is also referred to as a groove or a slit (slit groove).
  • the uneven structure in which metal plating is applied to the top surface and the side surface (excluding the bottom) is called a metal mask, and in some cases, is also called a diffraction grating forming precursor.
  • a high-aspect-ratio diffraction grating in which a concave portion having a desired depth is further formed by deeply etching a concave portion using the metal mask of the present invention.
  • Metal mask which is a precursor used for forming a high aspect ratio diffraction grating will be described.
  • the metal mask of the present invention 1) a first step of forming an aluminum layer on a silicon substrate; 2) applying a resist on the aluminum layer, patterning the resist, and then patterning the aluminum layer; 3) a third step of etching the silicon substrate corresponding to the region from which the aluminum layer has been removed to form a lattice having an uneven structure; 4) a fourth step of filling the recesses of the lattice with an organic material and solidifying to form an etching resist; 5) a fifth step of removing the organic material by an etching method while leaving the bottom of the concave portion; 6) a sixth step of applying metal plating to the upper surface and the side surfaces from which the organic material has been removed; 7) a seventh step of removing the organic material left on the bottom of the concave portion; It is manufactured through
  • the metal mask of the present invention is composed of a silicon substrate having a metal structure on an upper surface portion and a side surface portion and having a concavo-convex structure, a groove width in a range of 1 to 50 ⁇ m, and a depth of a groove of the concave portion. Has an uneven structure in the range of 1 to 150 ⁇ m.
  • FIG. 1 is a schematic sectional view showing an example of the entire configuration of a metal mask provided with metal plating of the present invention.
  • the metal mask 1 of the present invention includes a plurality of convex portions 5 and concave portions 4 on a silicon substrate 3.
  • An aluminum layer 2 which is a mask member used when forming the concave portion 4 is formed on the upper portion of the convex portion 5.
  • the metal mask 1 of the present invention the upper surface metal plating portion M on the upper surface of the projecting portion 5 is formed, a side metal plating portion M S of the convex portion 5 is formed in a region excluding the bottom portion 6 of the side surface portion I have.
  • the present invention is characterized in that there is no metal plating on the bottom.
  • the groove width W1 of the concave portion is preferably in the range of 1 to 50 ⁇ m, and the depth d1 of the groove of the concave portion is preferably in the range of 1 to 150 ⁇ m.
  • Components and manufacturing method of metal mask 2A to 2D and 3A to 3C are schematic views showing an example of a manufacturing process of a metal mask provided with metal plating, and the details of the manufacturing method of the metal mask will be described with reference to the drawings.
  • P-type silicon is preferably used as a silicon substrate used for manufacturing the metal mask of the present invention.
  • the use of P-type silicon is suitable for forming the metal component of the diffraction grating in the recess by applying an electroforming method.
  • an aluminum layer 2 is formed on a silicon substrate 3.
  • the aluminum layer 2 functions as a mask member when forming the concave portion 4 by etching in a specific position of the silicon substrate 3 in the next step (third step: FIG. 2C), and the etching process in the etching step It is made of aluminum, which is a material having resistance to the above.
  • the aluminum layer 2 is formed on the silicon substrate 3.
  • the aluminum layer 2 is formed by a dry film forming method such as a vacuum evaporation method or a sputtering method.
  • a resist is applied on the aluminum layer 2 by a spin coating method or the like.
  • RIE reactive ion etching
  • the aluminum layer 2 is formed on the silicon substrate 3 in the first step.
  • a resist is applied on the aluminum layer 2 by a spin coating method or the like, and the resist is formed into a slit (L / S shape) having a predetermined width by using an electron beam drawing apparatus (EB drawing). Perform patterning.
  • EB drawing electron beam drawing apparatus
  • the aluminum layer 2 is patterned (etched).
  • an Al etchant manufactured by Kanto Chemical Co., Ltd. can be used.
  • a positive photoresist or a negative photoresist can be used.
  • Known materials can be used as the positive photoresist and the negative photoresist.
  • ZPN-1150-90 manufactured by Zeon Corporation can be used.
  • OEBR-CAP112PM manufactured by Tokyo Ohka Kogyo Co., Ltd. can be used.
  • the silicon substrate 3 is etched by ICP (Inductively Coupled Plasma) dry etching from the surface of the silicon substrate 3 to a predetermined depth H,
  • the recess 4 is formed.
  • the shape of the recess 4 is preferably a recess structure in which the groove width is in the range of 1 to 50 ⁇ m and the depth of the groove of the recess 4 is in the range of 1 to 150 ⁇ m.
  • the photoresist layer is removed by the ICP dry etching. At this time, the aluminum layer 2 may be slightly etched.
  • the thickness of the aluminum layer 2 is reduced from, for example, about 150 nm to about 130 nm by ICP dry etching.
  • This ICP dry etching is a method capable of forming a concave portion having a high aspect ratio by vertical etching, and is preferably an ASE process using an ICP apparatus.
  • the ASE (Advanced Silicon Etch) process includes a process of etching a silicon substrate by RIE (reactive ion etching) using F radicals and F ions in SF 6 plasma, and a process of etching CF x radicals in C 4 F 8 plasma.
  • RIE reactive ion etching
  • the step of depositing a polymer film having a composition close to Teflon (registered trademark) on the wall surface by the polymerization reaction of these ions to act as a protective film is repeatedly performed.
  • etching such as so-called parallel plate type reactive ion etching (RIE), magnetic neutral plasma (NLD) dry etching, chemically assisted ion beam (CAIB) etching, and electron cyclotron resonance type reactive ion beam (ECRIB) etching It may be technology.
  • RIE parallel plate type reactive ion etching
  • NLD magnetic neutral plasma
  • CAIB chemically assisted ion beam
  • ECRIB electron cyclotron resonance type reactive ion beam
  • the organic material 7 that fills the recesses to form the etching resist is not particularly limited, but the following organic materials are preferable.
  • organic material applicable to the present invention examples include quinonediazides such as naphthoquinonediazide and benzoquinonediazide, diazo compounds such as diazomethyldrum acid, diazodimedone, 3-diazo-2,4-dione, and o-nitrobenzyl.
  • quinonediazides such as naphthoquinonediazide and benzoquinonediazide
  • diazo compounds such as diazomethyldrum acid, diazodimedone, 3-diazo-2,4-dione, and o-nitrobenzyl.
  • a photodegradation agent such as a mixture of an ester, an onium salt, an onium salt, polyphthalaldehyde, and t-butyl cholate; an alkali-soluble hydroquinone having an OH group; phloroglucin; -Mixtures of monomers such as trihydroxybenzophenone, novolak resins such as phenol novolak resin and cresol novolak resin, copolymers of styrene with maleic acid and maleimide, and copolymers of phenol with methacrylic acid, styrene and acrylonitrile.
  • condensate are polymethyl methacrylate, polymethyl methacrylate, polyhexafluorobutyl methacrylate, polydimethyl dimethyl tetrafluoropropyl methacrylate, trichloroethyl polymethacrylate, methyl methacrylate-acrylonitrile copolymer, polymethyl isopropenyl ketone, poly ⁇ - Examples include cyanoacrylate and polytrifluoroethyl- ⁇ -chloroacrylate. Among these, a mixed / condensed product containing a novolak resin as a main component is preferably used from the viewpoint of versatility.
  • organic materials are also available as commercial products.
  • a semiconductor coating material “Sumiresin Excel® CRC-8000 series” manufactured by Sumitomo Bakelite, for example, CRC-8200, CRC-8300 can be used.
  • OFPR-800, TSMR-V90, TMMR @ S2000, PMER-900, etc. manufactured by Tokyo Ohka Kogyo can be used.
  • ELPAC @ WPR series manufactured by JSR, for example, WPR-1020 can be used.
  • a positive-type insulating film “ZEOCOAT series” manufactured by Zeon Corporation for example, “ZPP2400, ZPP2500, ZPP2600, ZPP2700 series” of a positive photoresist “ZEONREX” for TFT manufacturing can be used.
  • "NPR9000, $ 7800, $ 8000 series” manufactured by Nagase ChemteX can be used.
  • “AZFP Series” manufactured by AZ Electronic Materials for example, TFP-650F5, TFP-650H2, and “AZ @ SR Series”, for example, AZ @ SR-100, AZ @ SR-110, AZ @ SR-210, and “AZ @ SFP Series”
  • AZ SFP-1400, AZ SFP-1500, etc. can be used.
  • solvents for the preparation of the recess filling liquid using an organic material, propylene glycol monomethyl ether, propylene glycol monoethyl ether, methyl cellosolve, methyl cellosolve acetate, ethyl cellosolve, ethyl cellosolve acetate, dimethylformamide, Dimethyl sulfoxide, dioxane, acetone, cyclohexanone, trichloroethylene, methyl ethyl ketone and the like can be mentioned. These solvents are used alone or in combination of two or more.
  • a coating solution prepared from the organic material and the solvent is appropriately selected from a conventionally known wet coating method, and a slit-shaped concave portion is formed by utilizing a capillary phenomenon or the like. And then heating and drying under desired conditions.
  • the method of removing the organic material 7 while leaving only the bottom 6 is not particularly limited, but it is preferable to remove the organic material 7 by acetone or oxygen plasma treatment.
  • a method for removing the organic material using acetone a method in which the silicon substrate 3 filled with the organic material is immersed in an acetone solution for a predetermined time, or a method in which acetone is supplied from the surface of the silicon substrate to a predetermined depth.
  • a method of removing the organic material can be mentioned.
  • the following method can be mentioned as the oxygen plasma treatment.
  • an organic material 7 filled in the recess 4 is irradiated with an oxygen plasma 10 having a strong oxidizing power for an organic substance from an oxygen plasma device 9 disposed on the upper portion of the silicon substrate 3.
  • the other organic materials are decomposed and removed, leaving only the material 8.
  • the surface of the organic material is irradiated with oxygen (oxygen radicals) in a high energy state, is bonded to carbon constituting the organic material, and is vaporized and decomposed (carbonized, ashing) as CO 2 .
  • oxygen oxygen radicals
  • a single gas or a mixed gas that generates oxygen plasma is used as a main component.
  • an oxygen atom-containing gas such as oxygen, carbon monoxide, and carbon dioxide can be used.
  • a mixed gas helium, nitrogen, and argon are used as long as the generation of oxygen plasma is not suppressed.
  • Any known gas such as an inert gas such as an inert gas, a chlorine-based gas, a fluorine-based gas, a hydrogen gas, or an ammonia gas may be appropriately mixed.
  • the thickness of the organic material 8 remaining on the bottom 6 is not particularly limited, but is preferably in the range of 10 to 50%, more preferably in the range of 15 to 30% of the depth of the groove of the concave portion. It is.
  • metal plating is applied to the upper surface of the convex portion 5 and the side surface of the concave portion 4 excluding the bottom portion 6 forming the silicon substrate 3 formed according to the above method, and as shown in FIG. to form a T and the side surface metal plating unit M S.
  • the formation of the metal plating layer M T and M S is preferably applied electroforming method (electroplating).
  • FIG. 4 is a schematic view showing an example of a method for forming a metal plating layer by an electroforming method applicable to the present invention.
  • the cathode of the power supply 13 is connected to the silicon substrate 3, and the anode electrode 12 connected to the anode of the power supply 13 and the silicon substrate 3 are immersed in the plating solution 11.
  • the surface of the silicon substrate 3 is hydrophilized by a method such as alkali treatment, or the ultrasonic wave is applied while the silicon substrate 3 is immersed in the plating solution 11.
  • the air in the concave portion 4 is evacuated, and the substrate is immersed in the plating solution 11 in this state.
  • a process such as evacuating the air in the concave portion 4 by vacuum defoaming in the immersed state may be performed.
  • examples of the metal used for metal plating include gold (Au), platinum (Pt), rhodium (Rh), ruthenium (Ru), iridium (Ir), indium (In), and nickel (Ni). And preferably nickel (Ni).
  • the thickness of the metal plating layer is not particularly limited, but is generally in the range of 10 to 500 nm, preferably in the range of 100 to 300 nm.
  • the acetone or oxygen plasma treatment used in the fifth step shown in FIG. 3A or a combination of the two methods can be used. After the organic material remaining on the bottom is removed by using this, oxygen ashing by oxygen plasma treatment is further performed to perform a cleaning process for completely removing the residue of the organic material on the bottom.
  • the metal mask 1 in which the metal plating is applied to the side surfaces except the top surface and the bottom of the projection is manufactured.
  • a high aspect ratio diffraction grating is manufactured using the manufactured metal mask.
  • the present invention is characterized in that a high aspect ratio diffraction grating is manufactured according to the following steps.
  • the etching method the method described when etching the silicon substrate shown in FIG. 2C as the third step of the metal mask 1 can be applied.
  • the etching apparatus E is further deep-etched by ICP (Inductively Coupled Plasma) dry etching, and the deeply recessed part 4B is formed.
  • ICP Inductively Coupled Plasma
  • the shape of the deep recess 4B is preferably an uneven structure in which the groove width is in the range of 1 to 50 ⁇ m, but the depth of the groove of the deep recess is in the range of 300 to 500 ⁇ m.
  • a groove of a concave portion having a high aspect ratio can be formed by a vertical etching method.
  • an ASE process using an ICP apparatus can be given.
  • the ASE (Advanced Silicon Etch) process includes a process of etching a silicon substrate by RIE (reactive ion etching) using F radicals and F ions in SF 6 plasma, and a process of etching CF x radicals in C 4 F 8 plasma.
  • the step of depositing a polymer film having a composition close to Teflon (registered trademark) on the wall surface by the polymerization reaction of these ions to act as a protective film is repeatedly performed.
  • the SF 6 plasma-rich state and the C 4 F 8 plasma-rich state alternate, as in the Bosch process.
  • a method is preferable in which the side wall protection and the bottom etching are alternately advanced by repeating.
  • the dry etching method is not limited to the ICP dry etching, but may be another method.
  • etching such as so-called parallel plate type reactive ion etching (RIE), magnetic neutral plasma (NLD) dry etching, chemically assisted ion beam (CAIB) etching, and electron cyclotron resonance type reactive ion beam (ECRIB) etching It may be technology.
  • an insulating layer is formed on the surface of the silicon substrate 3 on the side having the uneven structure and the surface of the concave portion.
  • the upper surface insulating layer 17T is provided on the upper surface of the convex portion 5 having the concavo-convex structure formed on the silicon substrate 3
  • the side insulating layer 17S is provided on the side surface of the convex portion 5
  • the bottom insulating layer 17B is provided on the bottom of the concave portion
  • an insulating layer 17 is formed around the silicon substrate 3 as necessary.
  • the insulating layer plays a role of controlling a metal component in the concave portion, for example, a metal plating process (electroforming process) for forming an X-ray shielding portion so that unnecessary plating growth does not occur in a later process.
  • a metal plating process electroforming process
  • a thermal oxidation method, an anodic oxidation method, a CVD method, a sputtering method, an evaporation method, or the like can be applied.
  • an example of a method for forming an insulating layer will be described.
  • An insulating layer 17 having a predetermined thickness is formed on the entire upper surface of the silicon substrate 3 and the entire inner surface of the concave portion 4B by thermal oxidation so as to be insulative to an electroforming process of an electroforming process for forming a metal component described later. Is formed.
  • the insulating layer 17 is a silicon oxide film because the silicon substrate 3 is used, and the silicon oxide film as the insulating layer 17 is formed with a thickness of, for example, about 150 nm.
  • This silicon oxide film is formed on at least the upper surface insulating layer 17T, the side surface insulating layer 17S of the concave portion 4B, and the bottom insulating layer 17B of the silicon substrate 3, but may also be formed on the back surface or side surface of the silicon substrate 3.
  • an oxide film is grown from the surface of the silicon substrate 3 which is a material to be oxidized by heating the uneven portion of the silicon substrate 3 in a gaseous atmosphere of oxygen or water vapor. An oxide film having good adhesiveness integrated with the above-mentioned material can be obtained.
  • the film thickness can be controlled with high accuracy by adjusting the flow rate of the gas atmosphere and the heating time. A membrane can be easily obtained.
  • a silicon substrate 3 which is a conductive material to be oxidized, is immersed in an electrolytic solution, and the material is used as an anode (positive electrode, positive electrode).
  • an oxide film is grown from the surface of the material.
  • the anodic oxidation method is very dense because the film formation proceeds as described above, An oxide film having good adhesion integrated with the material can be obtained.
  • the thickness of the oxide film is proportional to the applied voltage.
  • this anodic oxidation method is suitable as a method for forming an insulating film in the electroforming method in the electroforming step.
  • TEOS tetraethoxysilane
  • the carrier gas is used.
  • the bubbling generates a TEOS gas, and the TEOS gas is mixed with an oxidizing gas such as oxygen and ozone and a diluent gas such as helium to generate a source gas.
  • this source gas is introduced into a CVD apparatus such as a plasma CVD apparatus or a normal temperature ozone CVD apparatus, and a predetermined thickness (for example, about 40 nm) is formed as an insulating layer 17 on the surface of the silicon substrate 3 in the CVD apparatus.
  • a silicon oxide film is formed.
  • an alumina film having a predetermined thickness is formed as the insulating layer 17 by CVD. Since this CVD is a surface chemical reaction of a raw material gas, a dense film can be formed on the inner wall of the structure (in this embodiment, the inner surface of the slit groove SD) without any special measures.
  • a film having a thickness of several nm to several ⁇ m can be formed relatively easily.
  • insulating layer 17 is formed by deposition by sputtering, for example, a target of a substance (for example, quartz or alumina) to be formed as the insulating layer 17 is placed in a vacuum chamber, and a high voltage is applied.
  • a rare gas element such as argon (usually using argon) thus ionized is irradiated and collides with the target. Due to this collision, atoms on the surface of the target are repelled (sputtered).
  • the repelled atoms (sputtering particles) reach each surface of the uneven portion of the silicon substrate, the sputtered particles accumulate and deposit on the surface on the main surface side to form an insulating layer.
  • a silicon substrate 3 is arranged so as to face a substance (an evaporation source) to be formed as an insulating layer 17 in a vacuum chamber, and is generated by heating the evaporation source.
  • the gaseous film-forming material evaporation material
  • the gaseous film-forming material is irradiated to the surface on the main surface side.
  • the vapor deposition material reaches the surface on the main surface side, the vapor deposition material is deposited and deposited on the surface on the main surface side to form a film.
  • the vacuum deposition method is usually performed under a reduced pressure of about 10 ⁇ 2 to 10 ⁇ 4 Pa, the mean free path of the deposition material is as long as about several tens of cm to several tens of meters, and the silicon substrate 3 has almost no collision.
  • the vaporized substance vaporized from the vapor deposition source to reach the temperature has extremely good directivity. Therefore, a uniform and dense insulating layer can be formed deep inside the inner surface of the recess 4B having a relatively high aspect ratio.
  • a CVD method As a method for forming the protective mask 18, a CVD method, a sputtering method, an evaporation method, or the like can be applied. Among them, a thick silicon oxide film (SiO 2 layer) is formed by a chemical vapor deposition method (CVD method). Is preferred, for example, using tetraethoxysilane (TEOS) and a CVD device such as a plasma CVD device or a normal temperature ozone CVD device.
  • TEOS tetraethoxysilane
  • the bottom insulating layer 17B formed at the bottom of the concave portion is removed by using the same etching apparatus E used in the deep digging step.
  • a high-aspect-ratio diffraction grating 20 can be manufactured by filling the inside of the recess with a metal component 21 by using an electroforming method.
  • the metal component 21 is formed by applying a voltage to the silicon substrate 3 by an electroforming method (electroplating method) as shown in FIG. Then, the metal component 21 is filled in the recess.
  • the cathode of the power supply 13 is connected to the silicon substrate 3, and the anode electrode 12 connected to the anode of the power supply 13 and the silicon substrate 3 are applied to the plating solution 11. Soaked.
  • the metal component 21 precipitates and grows from the bottom surface of the concave portion by electroforming. Then, when the metal component 21 fills the inside of the slit-shaped concave portion, the electroforming ends.
  • the silicon component and the insulating layer function to transmit X-rays
  • the slit-shaped metal component 21 formed in the plurality of recesses functions to absorb X-rays.
  • a metal that absorbs X-rays is suitably selected.
  • a metal or a noble metal of an element having a relatively heavy atomic weight more specifically, for example, gold (Au), platinum ( Pt), rhodium (Rh), ruthenium (Ru) and iridium (Ir).
  • FIG. 7 is a schematic sectional view showing an example of the entire configuration of a high aspect ratio diffraction grating produced by the above method
  • FIG. 8 is a schematic perspective view thereof.
  • the feature of the high aspect ratio diffraction grating 20 of the present invention is that the recessed portion filled with the metal component 21 has a deeply recessed portion which is not conventionally available, in which the depth d4 is in the range of 300 to 500 nm.
  • the feature is that.
  • a diffraction grating having an extremely deep concave structure can be manufactured, and as a result, an X-ray shielding portion composed of a thick metal component can be formed.
  • an X-ray imaging apparatus having high resolution can be realized.
  • the metal plating Ms is formed on the side wall of the upper surface of the convex portion which is easily damaged by the etching in the deep digging process as described with reference to FIG.
  • a high aspect ratio diffraction structure having a stable uneven structure can be obtained. That is, even in a deep concave-convex structure having a depth of 300 ⁇ m or more, a convex portion having a desired shape can be formed without receiving damage to the distal end portion.
  • the high aspect ratio diffraction grating of the present invention can be applied to a Talbot-Lau interferometer.
  • FIG. 10 is a schematic configuration diagram showing an example of the configuration of an X-ray Talbot-Lau interferometer to which the high aspect ratio diffraction grating of the present invention is applied.
  • the Talbot-Lau interferometer 50 includes an X-ray source 51, a multi-slit plate G0, a first diffraction grating G1, and a second diffraction grating G2, as shown in FIG.
  • the multi-slit plate G0 shown in FIG. 10 is the high aspect ratio diffraction grating 20 of the present invention.
  • the high aspect ratio diffraction grating 20 of the present invention which is the multi-slit plate G0, is radiated from the X-ray source 51. X-rays can be more reliably used as a multiple light source.
  • the amount of X-ray radiated toward the first diffraction grating G1 via the subject S is increased as compared with the Talbot interferometer, so that a higher sharpness and better moiré fringes are obtained. Is obtained.
  • the high aspect ratio diffraction grating of the present invention can be used for various optical devices, it is possible to form the metal portion 21 having a high aspect ratio and a sufficient thickness. Can be suitably used.
  • Preparation of diffraction grating >> [Production of diffraction grating 1] (Production of metal mask) ⁇ 1: Formation of aluminum layer on silicon substrate> A 400 nm-thick aluminum layer was formed on the P-type silicon wafer by performing a sputtering process for 30 minutes at a DC power of 500 W using a modified sputtering machine SIH-450 manufactured by ULVAC (see FIG. 2A).
  • ⁇ Patterning of resist> After applying a resist on the aluminum layer by a spin coating method, the resist was patterned into a slit shape (L / S shape) with a width of 10 ⁇ m using an electron beam lithography apparatus (EB lithography) under the following conditions.
  • EB lithography electron beam lithography apparatus
  • Exposure was performed at 6.1 ⁇ J / cm 2 using an electron beam direct writing apparatus F5112 manufactured by Advantest Corporation as an electron beam writing apparatus (EB writing).
  • OEBR-CAP112PM manufactured by Tokyo Ohka Kogyo Co., Ltd. was used as the resist.
  • the spin coating was performed at 2500 rpm for 60 seconds.
  • ⁇ 2 Patterning of aluminum layer> The aluminum layer was patterned using the patterned resist as a mask. The etching of the aluminum layer was performed under the following conditions using an Al etchant manufactured by Kanto Chemical Co. (see FIG. 2B).
  • etching solution AI etchant
  • etching by dipping at room temperature of 25 ° C. was performed for about 5 minutes.
  • pure water washing was performed three times to remove the etching solution.
  • Conditions during etching using ASE-Pegasus was performed RF1800W, platen180W, APC4.5Pa, in SF 6 gas300sccm at 6.7 S.
  • the conditions for forming the protective film were RF 1800 W, platen 180 W, APC 3.5 Pa, C 4 F 8 gas 150 sccm, and 3.1 s. This was alternately performed 50 cycles to obtain a structure having a depth of 60 ⁇ m.
  • ⁇ 6 Metal plating on top and side surfaces> The silicon wafer from which the organic material other than the bottom of the recess was removed was subjected to electroplating (electroforming) by the electroforming method having the configuration shown in FIG. Using a gold (Au) solution as a plating solution, a plating process is performed for 5 minutes at a constant current of 1 mA, and gold (Au) is applied to the upper surface of the protrusion and the side surface (height 50 ⁇ m) excluding the bottom inside the recess. Was plated with a metal having a thickness of 200 nm (see FIG. 3B).
  • Au gold
  • ⁇ 8 Deep digging> Next, deep digging for forming a diffraction grating was performed using the metal mask prepared above. Specifically, etching was performed using a mass production silicon excavator ASE-Pegasus manufactured by SPTS to produce a high aspect ratio uneven structure having a groove width W1 of 10 ⁇ m and a groove depth d4 of 300 ⁇ m (FIG. 5B).
  • insulating layer Formation of insulating layer> Then, the obtained high-aspect-ratio uneven structure is subjected to a thermal oxidation treatment, so that a 140-nm-thick insulating film made of SiO 2 is formed on the upper surface of the uneven structure, the side surface of the concave portion, and the peripheral portion of the silicon wafer. A layer was formed. The thermal oxidation treatment was performed at 1080 ° C. for 2 hours (see FIG. 6A).
  • Sputtering was performed by using a sputtering machine manufactured by Osaka Vacuum Co., Ltd. at RF of 300 W and 0.1 Pa for 15 minutes to form an upper surface mask layer of SiO 2 to a thickness of 105 nm.
  • ⁇ 13 Filling of metal component into recess> Then, a gold component is grown from the inside of the concave portion using a gold plating solution by the electroplating method shown in FIG. 4, and the entire inside of the concave portion is filled with gold. Lattice 1 was made.
  • a gold plating solution (Microfab Au660) manufactured by Tanaka Kikinzoku Co., Ltd., plating was performed at a current density of 1.5 mA / cm 2 for 90 hours. The solution temperature of the gold plating solution was maintained at 55 ° C.
  • a diffraction grating 2 was produced in the same manner as in the production of the diffraction grating 1 except that the following conditions were changed.
  • the depth d4 of the grooves of the diffraction grating in ⁇ 8: Deep digging> was changed to 400 nm.
  • a diffraction grating 3 was produced in the same manner as in the production of the diffraction grating 1 except that the following conditions were changed.
  • the depth d1 of the groove of the metal mask in ⁇ 3: formation of concave portion: Bosch process> was changed to 100 ⁇ m.
  • the oxygen ashing time in ⁇ 5: Removal of organic material> was changed to 50 minutes.
  • the plating metal type in ⁇ 6: metal plating on top and side surfaces> was changed to copper (Cu).
  • the depth d4 of the grooves of the diffraction grating in ⁇ 8: deep digging> was changed to 500 nm.
  • Diffraction gratings 4 to 6 were produced in the same manner as in the production of diffraction gratings 1 to 3, except that the groove width W1 of the metal mask was changed from 10 ⁇ m to 20 ⁇ m.
  • Diffraction gratings 7 to 9 were produced in the same manner as in the production of diffraction gratings 1 to 3, except that the metal plating treatment in ⁇ 6: Application of metal plating to upper surface and side surfaces> was not performed.
  • the metal mask of the present invention can be applied to the manufacture of a high aspect ratio diffraction grating, and this high aspect ratio diffraction grating can be suitably used for a Talbot interferometer or a Talbot-Lau interferometer.

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Abstract

La présente invention concerne un procédé de fabrication d'un masque métallique qui a une résistance contre la gravure et un masque métallique obtenu par ce procédé, et un procédé de fabrication d'un réseau de diffraction à rapport d'aspect élevé qui a une résolution élevée à l'aide du masque métallique et un réseau de diffraction à rapport d'aspect élevé obtenu par ce procédé. Ce procédé de fabrication d'un masque métallique est caractérisé par les étapes consistant à : fabriquer un masque métallique en formant une couche d'aluminium sur un substrat de silicium, former des motifs sur la couche d'aluminium, graver le substrat de silicium qui correspond à la région dont la couche d'aluminium a été éliminée pour former un réseau ayant une structure irrégulière, remplir des évidements du réseau d'un matériau organique et solidifier celui-ci pour former une réserve de gravure, éliminer le matériau organique par un procédé de gravure à l'exception des parties inférieures des évidements, métalliser la surface supérieure et la surface latérale dont le matériau organique a été éliminé, et éliminer le matériau organique restant dans les parties inférieures des évidements.
PCT/JP2019/025524 2018-07-19 2019-06-27 Procédé de fabrication de masque métallique et masque métallique, et procédé de fabrication de réseau de diffraction à rapport d'aspect élevé et réseau de diffraction à rapport d'aspect élevé WO2020017270A1 (fr)

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Cited By (1)

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Publication number Priority date Publication date Assignee Title
CN111916330A (zh) * 2020-07-02 2020-11-10 中国科学院上海光学精密机械研究所 光栅深刻蚀的方法

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JP2002200598A (ja) * 2000-10-17 2002-07-16 Robert Bosch Gmbh マイクロメカニカル素子およびその製法
JP2006011129A (ja) * 2004-06-28 2006-01-12 Canon Inc 微細構造を有する光学素子の製造方法。
WO2012176728A1 (fr) * 2011-06-23 2012-12-27 旭化成株式会社 Stratifié pour la formation d'un motif fin, et procédé de production d'un stratifié pour la formation d'un motif fin
JP5353101B2 (ja) * 2008-07-29 2013-11-27 大日本印刷株式会社 微細構造体形成方法
US20160314981A1 (en) * 2015-04-27 2016-10-27 Samsung Electronics Co., Ltd. Methods for forming pattern using cyclic processing
JP2017163032A (ja) * 2016-03-10 2017-09-14 東芝メモリ株式会社 半導体装置の製造方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002200598A (ja) * 2000-10-17 2002-07-16 Robert Bosch Gmbh マイクロメカニカル素子およびその製法
JP2006011129A (ja) * 2004-06-28 2006-01-12 Canon Inc 微細構造を有する光学素子の製造方法。
JP5353101B2 (ja) * 2008-07-29 2013-11-27 大日本印刷株式会社 微細構造体形成方法
WO2012176728A1 (fr) * 2011-06-23 2012-12-27 旭化成株式会社 Stratifié pour la formation d'un motif fin, et procédé de production d'un stratifié pour la formation d'un motif fin
US20160314981A1 (en) * 2015-04-27 2016-10-27 Samsung Electronics Co., Ltd. Methods for forming pattern using cyclic processing
JP2017163032A (ja) * 2016-03-10 2017-09-14 東芝メモリ株式会社 半導体装置の製造方法

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111916330A (zh) * 2020-07-02 2020-11-10 中国科学院上海光学精密机械研究所 光栅深刻蚀的方法

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