US3742230A - Soft x-ray mask support substrate - Google Patents
Soft x-ray mask support substrate Download PDFInfo
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- US3742230A US3742230A US00267672A US3742230DA US3742230A US 3742230 A US3742230 A US 3742230A US 00267672 A US00267672 A US 00267672A US 3742230D A US3742230D A US 3742230DA US 3742230 A US3742230 A US 3742230A
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- 239000012528 membrane Substances 0.000 claims abstract description 103
- 239000006096 absorbing agent Substances 0.000 claims abstract description 39
- 230000002093 peripheral effect Effects 0.000 claims abstract description 17
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 162
- 229910052710 silicon Inorganic materials 0.000 claims description 162
- 239000010703 silicon Substances 0.000 claims description 162
- 239000000463 material Substances 0.000 claims description 37
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 21
- 229910052796 boron Inorganic materials 0.000 claims description 21
- 238000004519 manufacturing process Methods 0.000 claims description 20
- 238000005530 etching Methods 0.000 claims description 18
- 229910052785 arsenic Inorganic materials 0.000 claims description 17
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims description 17
- 229910052782 aluminium Inorganic materials 0.000 claims description 16
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 16
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 11
- 229910052733 gallium Inorganic materials 0.000 claims description 11
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 claims description 11
- 229910052787 antimony Inorganic materials 0.000 claims description 9
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 9
- 238000000151 deposition Methods 0.000 claims description 8
- 239000010410 layer Substances 0.000 description 79
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 18
- 238000000034 method Methods 0.000 description 14
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 11
- 239000010931 gold Substances 0.000 description 11
- 229910052737 gold Inorganic materials 0.000 description 11
- 235000012239 silicon dioxide Nutrition 0.000 description 9
- 239000000377 silicon dioxide Substances 0.000 description 9
- 229910052581 Si3N4 Inorganic materials 0.000 description 7
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 7
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 6
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 229910052790 beryllium Inorganic materials 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 238000001015 X-ray lithography Methods 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000010894 electron beam technology Methods 0.000 description 2
- 239000011241 protective layer Substances 0.000 description 2
- 238000007665 sagging Methods 0.000 description 2
- 239000011343 solid material Substances 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000012777 commercial manufacturing Methods 0.000 description 1
- IDLFZVILOHSSID-OVLDLUHVSA-N corticotropin Chemical compound C([C@@H](C(=O)N[C@@H](CO)C(=O)N[C@@H](CCSC)C(=O)N[C@@H](CCC(O)=O)C(=O)N[C@@H](CC=1NC=NC=1)C(=O)N[C@@H](CC=1C=CC=CC=1)C(=O)N[C@@H](CCCNC(N)=N)C(=O)N[C@@H](CC=1C2=CC=CC=C2NC=1)C(=O)NCC(=O)N[C@@H](CCCCN)C(=O)N1[C@@H](CCC1)C(=O)N[C@@H](C(C)C)C(=O)NCC(=O)N[C@@H](CCCCN)C(=O)N[C@@H](CCCCN)C(=O)N[C@@H](CCCNC(N)=N)C(=O)N[C@@H](CCCNC(N)=N)C(=O)N1[C@@H](CCC1)C(=O)N[C@@H](C(C)C)C(=O)N[C@@H](CCCCN)C(=O)N[C@@H](C(C)C)C(=O)N[C@@H](CC=1C=CC(O)=CC=1)C(=O)N1[C@@H](CCC1)C(=O)N[C@@H](CC(N)=O)C(=O)NCC(=O)N[C@@H](C)C(=O)N[C@@H](CCC(O)=O)C(=O)N[C@@H](CC(O)=O)C(=O)N[C@@H](CCC(O)=O)C(=O)N[C@@H](CO)C(=O)N[C@@H](C)C(=O)N[C@@H](CCC(O)=O)C(=O)N[C@@H](C)C(=O)N[C@@H](CC=1C=CC=CC=1)C(=O)N1[C@@H](CCC1)C(=O)N[C@@H](CC(C)C)C(=O)N[C@@H](CCC(O)=O)C(=O)N[C@@H](CC=1C=CC=CC=1)C(O)=O)NC(=O)[C@@H](N)CO)C1=CC=C(O)C=C1 IDLFZVILOHSSID-OVLDLUHVSA-N 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 238000000206 photolithography Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000003362 replicative effect Effects 0.000 description 1
- 231100000925 very toxic Toxicity 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- 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
- G03F1/22—Masks or mask blanks for imaging by radiation of 100nm or shorter wavelength, e.g. X-ray masks, extreme ultraviolet [EUV] masks; Preparation thereof
-
- 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
- G21K1/10—Scattering devices; Absorbing devices; Ionising radiation filters
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
- Y10S430/167—X-ray
- Y10S430/168—X-ray exposure process
Definitions
- ABSTRACT A soft X-ray mask support substrate including a thick peripheral support structure; a thin, taut membrane, transparent to soft X-rays and carried by the support structure covering the area within the periphery; and a soft X-ray absorber layer arranged in a predetermined pattern on the membrane within the periphery of the support structure.
- This invention relates to a soft X-ray support substrate, and more particularly to such a substrate having a taut membrane transparent to soft X-rays for supporting a pattern in soft X-ray absorber material.
- Soft X-ray printing has been proposed as a technique for replicating sub-micron planar patterns, see Soft X-ray Lithographic Apparatus and Process, filed Jan. 15, 1972, Ser. No. 217,902; typically the pattern is generated by a scanning electron microscope.
- Soft X-ray exposure masks have been made for acoustic surface wave transducer patterns with 1.3 micron electrode spacing and have been successfully replicated.
- soft X-ray lithography has shown a resolution capability greater than that of ordinary photolithography and comparable to the highly sophisticated scanning electron microscope techniques.
- the simplicity and low cost of soft X-ray lithography indicate that it could have a significant impact on ultra-high resolution device fabrication in the future.
- Beryllium the solid material most transparent to soft X-rays, appears well suited for the supporting portion of the mask.
- the thinnest foil of beryllium commercially available was approximately 12 microns thick. The surface of this foil was irregular, having numerous pits of one micron depth, and was not suitable as a substrate on which high resolution, submicron patterns must be constructed in an absorber layer.
- beryllium is attacked by most acids (weak as well as strong) and by alkaline solutions, so a very serious corrosion and chemical compatibility problem exists with this material. Also beryllium dust is very toxic, so elaborate safety precautions must be taken if the material is cut or machined.
- the invention results from the realization that the dimpling or sagging problem would be solved by producing a tension in the membrane that would keep it taut and that such a tension could be produced in a thin silicon'membrane supported on a thicker silicon support structure by doping the membrane with boron or phosphorous which has a smaller covalent bond radius than silicon and therefore causes the membrane to shrink relative to the surrounding support structure of undoped silicon and further that such a tension could also be produced in thin silicon membrane supported on a thicker silicon support structure doped with arsenic, gallium, antimony or aluminum each of which has a larger covalent bond radius than silicon and therefore causes the support structure to expand relative to the undoped silicon membrane and stretch the membrane.
- the invention features a soft X-ray mask substrate including a wafer of a first material of which a thin layer is doped with a small percentage of a second material which contracts that thin layer of the first material slightly and reduces the attack rate of an etchant on the first material enough to create a thin, taut membrane of the doped material, transparent to soft X-rays to function as a pattern window and yet leave sufficient amounts of the first material in the remaining portion of the first material about the pattern window to act as a support structure.
- a soft X-ray mask substrate can be constructed using a thick layer of a first material doped with a small percentage of a second material which expands the first material slightly and on which is deposited a thin layer of the first material such that an etchant may selectively remove enough of the doped first material to create a thin, taut membrane of the undoped first material, transparent to soft X-rays to function as a pattern window, and yet leave sufficient amounts of the doped first material about the pattern window to act as a support structure.
- FIG. 1 is an elevational, schematic view of an initial step in the fabrication of a substrate according to this invention for supporting a soft X-ray mask.
- FIG. 2 is an elevational schematic view similar to that shown in FIG. 1 of a subsequent step in the fabrication of a soft X-ray mask support substrate according to this invention.
- FIG. 3 is an elevational schematic view similar to that of FIG. 2 of a further step in the fabricating of a soft X-ray mask support substrate according to this invention.
- FIG. 4 is an elevational schematic view similar to that of FIG. 3 of a completed soft X-ray mask support substrate according to this invention.
- FIG. 5 is a elevational, schematic view of an initial step in the fabrication of an alternative substrate according to this invention for supporting a soft X-ray mask.
- FIG. 6 is an elevational, schematic view similar to that of FIG. 5 of a subsequent step in the fabrication of FIG. 7 is an elevational, schematic view similar to 1 that of FIG. 6 of a further step in the fabrication of an alternative substrate according to this invention for supporting a soft X-ray mask.
- FIG. 8 is an elevational, schematic view similar to that of FIG. 7 of a completed soft X-ray mask support substrate according to this invention.
- FIG. 9 is a schematic, axonometric view of a soft X-ray mask support substrate with a plurality of pattern windows and membranes.
- a support substrate 6 for a soft X-ray mask 8 may be constructed, FIG. 1, using a single silicon wafer 10 of the N type or lightly doped P type approximately 200 microns in thickness. Wafer 10 is heavily diffused with boron such that a concentration of about 2 X10" cm exists at a depth of 3 microns from the surface forming boron diffusion layer 12.
- Silicon dioxide layers 14 and 16 each about 0.1 micron thick, FIG. 2, are then grown on the top and bottom of wafer 10. Silicon dioxide layers 14 and 16 function to provide a protective layer which prevents undesired chemical attack to the silicon. Following this the desired soft X-ray mask pattern 18, FIG. 3, is fabricated in pattern area 19 on silicon dioxide layer 16 using state of the art methods such as scanning electron beam technoogy or photolithographic techniques. Mask pattern 18 may be formed of gold or any other good soft X-ray absorber. In FIG. 3 a gold layer 20 0.3 micron thick is used and an intermediate layer 22 of chrominum 0.03 micron thick is used to improve the adherence between the gold layer 20 and the silicon dioxide layer 16. Oppositethe mask pattern 18 an opening 24 is etched in silicon dioxide layer.14 using an etchant such as buffered hydrofluoric acid which attacks the silicon dioxide layer 14 but not the silicon of wafer 10.
- an etchant such as buffered hydrofluoric acid which attacks the silicon dioxide layer 14 but not the silicon of wafer
- the wafer 10 is placed in a l 15C solution of 68 ml ethylene diamine, 12g pyrocatechol, and 32 ml water for about 1 15 hours.
- the solution etches away the bulk of the silicon beneath opening 24 in silicon dioxide layer 14 and creates a pattern window 26, FIG. 4, in the silicon wafer 10 which corresponds to the pattern area 18 which has been created on the opposite side of wafer 10 in the soft X-ray absorbing gold layer 20.
- This etchant only etches as far as the boron diffused layer 12 and no farther. In addition this etchant also does not attack the chromium or the gold portions.
- membrane 28 is formed from the portion of the boron diffused layer 12 which extends across pattern window 26.
- Membrane 28 is relatively thin i.e. approximately 3 microns in thickness corresponding in thickness to the boron diffused layer 12.
- membrane 28 is quite transparent to the soft X-rays which will be used to expose substrates through pattern area 18 of mask 8.
- this fabrication technique also introduces a tautness in membrane 28 because of the action of the boron doping in the medium of the silicon: a tension arises because of the slight decrease of the lattice constant produced by boron doping because boron has a smaller covalent bond radius than that of silicon. As a result the membrane 28 shrinks and becomes taut relative to the rest of the silicon substrate which is not doped with boron.
- this tautness or tension membrane 28 provides a very flat, rigid substrate for the gold absorber layer 20'and its intermediate layer 22; an added advantage of this technique is that the etchant which is used etches much more rapidly in the crystal direction l00 than it does in the direction 1 1 l and so the etching process moves much more quickly in the direction from silicon dioxide layer 14 towards boron diffused layer 12 than it does in the lateral direction transverse to that path so that window 26 is produced in an area beneath opening 24 without any serious undercutting at the sides of window 26 beneath the remaining portions of silicon dioxide layer 14. In fact the etching process provides sloping walls 32 and 34 which slant inwardly in window 26. A mask approximately 1 inch square having 49, 5 um thick pattern windows each 60 mils square has been made with no sagging of the membrane.
- Pattern 18 may be any type of micron-miniature circuit or system such as electronic circuits or micro sound circuits.
- Substrate 6 has a number of advantages: silicon is highly resistant to corrosion and since silicon technology is well developed high quality materials meeting precise specifications may be easily obtained. Further, since the entire substrate 6 including the support structure 30 and membrane 28 are made from the same single crystal, no adhesion problem exists and temperature changes will not distort membrane 28.
- a support substrate 6 for a soft X-ray mask 8' may be constructed, FIG. 5, using a single crystal silicon wafer 10' approximately 200 microns in thickness. Wafer 10 is heavily diffused with arsenic to a concentration of about 10" atoms/cm.
- a three micron epitaxial layer 40, FIG. 6, of pure silicon is grown on one surface and layers 14 and 16' of silicon nitride about one tenth of a micron thick are provided on both surfaces. Silicon nitride layers 14,
- FIG. 7 is fabricated in pattern area 19' of silicon nitride layer 16' using state of the art methods such as scanning electron beam lithograph or photoiithographic techniques.
- Mask pattern 18' may be formed of gold or any other good soft X-ray absorber. In FIG. 7 a gold layer 20 three tenths of a micron thick is used.
- an opening 24' is etched in the silicon nitride layer 14' using an etchant such as concentrated hydrofluoric acid which attacks the silicon nitride layer 14' but not the silicon of wafer
- an etchant such as concentrated hydrofluoric acid which attacks the silicon nitride layer 14' but not the silicon of wafer
- the wafer 10' is placed in a solution of one part hydrofluoric acid, three parts nitric acid and 10 parts acetic acid for about one and one half hours.
- This solution etches away the bulk of the arsenic doped silicon beneath opening 24 in silicon nitride layer 14 and creates a pattern window 26, FIG. 8, in the silicon wafer .10 which corresponds to the pattern area 18 which has been created on the opposite side of wafer 10' in the soft X-ray absorbing gold layer 20'.
- this fabrication technique also introduces a tautness in membrane 28' because of the action of the arsenic doping in the medium of the silicon: a tension arises because of the slight increase of the .lattice constant produced by arsenic doping because arsenic has a largercovalent bond radius than that of silicon.
- the support structure 30' expands relative to the silicon layer 40 which is not doped with arsenic and causes membrane 28' to become taut. Because of this tautness or tension membrane 28' provides a very flat, rigid substrate for the gold absorber layer 20'.
- substrate 6" roughly 1 inch square may contain 40 membranes 28" and forty pattern windows 26" each of which is roughly 65 mils square.
- a soft X-ray support substrate comprising: a thick silicon peripheral support structure; and a thin, taut, silicon membrane transparent to soft X-rays and carried by said support structure covering the area within the periphery of said support structure for carrying a soft X-ray absorber layer arranged in a predetermined pattern on said membrane within said periphery of said support structure; said membrane being doped with a material having a smaller covalent bond radius than silicon to shrink said membrane to produce tension in it and make it taut.
- a soft X-ray support substrate comprising: a thick silicon peripheral support structure; and a thin, taut, silicon membrane transparent to soft X-rays and carried by said support structure covering the area within the periphery of said support structure for carrying a soft X-ray absorber layer arranged in a predetermined pattern on said membrane within said periphery of said support structure; said membrane being doped with boron having a smaller covalent bond radius than silicon to shrink said membrane to produce tension in it and make it taut.
- a soft X-ray support substrate comprising: a thick silicon peripheral support structure; and a thin, taut, silicon membrane transparent to soft X-rays and carried by said support structure covering the area within the periphery of said support structure for carrying a soft X-ray absorber layer arranged in a predetermined pattern on said membrane within said periphery of said support structure; said membrane being doped with phosphorous having a smaller covalent bond radius than silicon to shrink said membrane to produce tension in it and make it taut.
- a soft X-ray support substrate comprising: a thick silicon peripheral support structure, and a thin, taut silicon membrane transparent to soft X-rays and carried by said support structure covering the area within the periphery of said support structure for carrying a soft X-ray absorber layer arranged in a predetermined pattern on said membrane within said periphery of said support structure; said support structure being doped with a material having a larger covalent bond radius than silicon to expand said support structure and produce tension in said membrane making it taut.
- a soft X-ray support substrate comprising: a thick silicon peripheral support structure, and a thin, taut silicon membrane transparent to soft X-rays and carried by said support structure covering the area within the periphery of said support structure for carrying a soft X-ray abosrber layer arranged in a predetermined pattern on said membrane within said periphery of said support structure; said support structure being doped with anitmony having a larger covalent bond radius than silicon to expand said support structure and produce tension in said membrane making it taut.
- a soft X-ray support substrate comprising: a thick silicon peripheral support structure, and a thin, taut silicon membrane transparent to soft X-rays and carried by said support structure covering the area within the periphery of said support structure for carrying a soft X-ray absorber layer arranged in a predetermined pattern on said membrane within said periphery of said support'structure; said support structure being doped with gallium having a larger covalent bond radius than silicon to expand said support structure and produce tension in said membrane making it taut.
- a soft X-ray support substrate comprising: a thick silicon peripheral support structure, and a thin, taut silicon membrane transparent to soft X-rays and carried by said support structure covering the area within the periphery of said support structure for carrying a soft X-ray absorber layer arranged in a predetermined pattern on said membrane within said periphery of said support structure; said support structure being doped with aluminum having a larger covalent bond radius than silicon to expand said support structure and produce tension in said membrane making it taut.
- a method of making a soft X-ray mask support substrate comprising: doping a first surface of a silicon substrate with boron toa predetermined thickness to shrink that doped portion of said silicon substrate; providing an etch resistant layer on the second surface of said substrate except in the area corresponding to the area on the first surface for carrying a predetermined pattern in soft X-ray absorber material; and subjecting the exposed said area of said second surface to an etchant which attacks the silicon of the support substrate and which is ineffective in etching the boron doped silicon and the etch resistant layer to create a window in the silicon substrate covered by a membrane formed from the boron doped silicon and kept taut by the shrinking of the boron doped silicon.
- a method of making a soft X-ray mask support substrate comprising: doping a first surface of a silicon substrate with phosphorous to a predetermined thickness to shrink that doped portion of said silicon substrate; providing an etch resistant layer on the second surface of said substrate except in the area corresponding to the area on the first surface for carrying a predetermined pattern in soft X-ray absorber material; and subjecting the exposed said area of said second surface to an etchant which attacks the silicon of the support substrate and which is ineffective in etching the phosphorous doped silicon and the etch resistant layer to create a window in the silicon substrate covered by a membrane formed from the phosphorous doped silicon and kept taut by the shrinking of the phosphorous doped silicon.
- a method of making a soft X-ray support substrate comprising:
- a method of making a soft X-ray support substrate comprising:
- a method of making a soft X-ray support substrate comprising:
- a method of making a soft X-ray support substrate comprising:
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- General Engineering & Computer Science (AREA)
- High Energy & Nuclear Physics (AREA)
- Exposure Of Semiconductors, Excluding Electron Or Ion Beam Exposure (AREA)
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Abstract
A soft X-ray mask support substrate including a thick peripheral support structure; a thin, taut membrane, transparent to soft Xrays and carried by the support structure covering the area within the periphery; and a soft X-ray absorber layer arranged in a predetermined pattern on the membrane within the periphery of the support structure.
Description
United States Patent [1 1' Spears et al.
[ SOFT X-RAY MASK SUPPORT SUBSTRATE [75] Inventors: David L. Spears, Acton; Henry I.
Smith, Sudbury; Ernest Stern, Concord, all of Mass.
[73] Assignee: Massachusetts Institute of Technology, Cambridge, Mass.
[22] Filed: June 29, 1972 [21] Appl. No.: 267,672
[52] U.S. Cl. 250/65 R, 250/49.5 TE, 250/105,
29/578, 96/384 [51] Int. Cl. G01n 21/34 [58] Field of Search 250/65 R, 49.5 TE; 7 96/362, 38.4; 29/578 [56] References Cited UNITED STATES PATENTS Hallman 250/65 R June 26, 1973 Primary Examiner-James W. Lawrence Assistant Examiner-l-laro1d A. Dixon Attorney-Joseph S. landiorio and Arthur A. Smith,
[5 7] ABSTRACT A soft X-ray mask support substrate including a thick peripheral support structure; a thin, taut membrane, transparent to soft X-rays and carried by the support structure covering the area within the periphery; and a soft X-ray absorber layer arranged in a predetermined pattern on the membrane within the periphery of the support structure.
16 Claims, 9 Drawing Figures FIELD OF INVENTION This invention relates to a soft X-ray support substrate, and more particularly to such a substrate having a taut membrane transparent to soft X-rays for supporting a pattern in soft X-ray absorber material.
I BACKGROUND OF INVENTION Soft X-ray printing has been proposed as a technique for replicating sub-micron planar patterns, see Soft X-ray Lithographic Apparatus and Process, filed Jan. 15, 1972, Ser. No. 217,902; typically the pattern is generated by a scanning electron microscope. Soft X-ray exposure masks have been made for acoustic surface wave transducer patterns with 1.3 micron electrode spacing and have been successfully replicated. Thus soft X-ray lithography has shown a resolution capability greater than that of ordinary photolithography and comparable to the highly sophisticated scanning electron microscope techniques. The simplicity and low cost of soft X-ray lithography indicate that it could have a significant impact on ultra-high resolution device fabrication in the future. However wide scale use of the soft X-ray technique especially as a commercial manufacturing approach will depend in part upon the ease with which large area masks can be made and can be aligned with the substrate or wafer to be exposed. Because of the high absorption coefficient of all solid materials to soft X-rays the supporting portion of the mask must be made quite thin in orderto have reasonable transparency.
Beryllium the solid material most transparent to soft X-rays, appears well suited for the supporting portion of the mask. However, the thinnest foil of beryllium commercially available was approximately 12 microns thick. The surface of this foil was irregular, having numerous pits of one micron depth, and was not suitable as a substrate on which high resolution, submicron patterns must be constructed in an absorber layer. In addition, beryllium is attacked by most acids (weak as well as strong) and by alkaline solutions, so a very serious corrosion and chemical compatibility problem exists with this material. Also beryllium dust is very toxic, so elaborate safety precautions must be taken if the material is cut or machined.
The problems encountered with beryllium suggest that a better material might be available. But any other material would be less transparent to soft X-rays and would require a much thinner layer of that material, which would tend to sag of its own weight. Some sort of support was therefore necessary to hold this thinner membrane.
Initial attempts in making a support involved bonding aluminum foil across a metal washer, and evaporating aluminum onto silicon and etching a hole in the silicon up to the aluminum. In all instances the membranes were not flat, but exhibited a large degree of warping. The amount of sag was dependent upon the temperature, due to the difference in thermal expansion of the aluminum and the support frame. The aluminum was also attacked by some of the chemicals to be used in later processing steps.
Another attempt involved using a wafer of silicon doped with phosphorus on which an epitaxial layer of pure silicon was grown, and etching away part of the phosphorus doped substrate up to the epitaxial layer. This membrane structure was chemically resistant, quite rugged and stable with temperature changes. However, the membrane was badly dimpled. Strain in the epitaxial layer was released when the phosphorus doped silicon was etched away resulting in a concave or convex structure. In some cases the membrane was dimpled inward by as much as ten microns. This was not suitable for a high resolution mask.
SUMMARY OF INVENTION It is therefore an object of this invention to provide a soft X-ray mask substrate which is thick enough in parts to be fully supporting yet thin enough in other parts to be relatively transparent to soft X-rays.
It is a further object of this invention to provide a soft X-ray mask substrate in which the thin area or membrane, which is relatively transparent to soft Xrays and on which a pattern is constructed in soft X-ray absorbent material, is taut and not disposed to sag or droop.
The invention results from the realization that the dimpling or sagging problem would be solved by producing a tension in the membrane that would keep it taut and that such a tension could be produced in a thin silicon'membrane supported on a thicker silicon support structure by doping the membrane with boron or phosphorous which has a smaller covalent bond radius than silicon and therefore causes the membrane to shrink relative to the surrounding support structure of undoped silicon and further that such a tension could also be produced in thin silicon membrane supported on a thicker silicon support structure doped with arsenic, gallium, antimony or aluminum each of which has a larger covalent bond radius than silicon and therefore causes the support structure to expand relative to the undoped silicon membrane and stretch the membrane.
The invention features a soft X-ray mask substrate including a wafer of a first material of which a thin layer is doped with a small percentage of a second material which contracts that thin layer of the first material slightly and reduces the attack rate of an etchant on the first material enough to create a thin, taut membrane of the doped material, transparent to soft X-rays to function as a pattern window and yet leave sufficient amounts of the first material in the remaining portion of the first material about the pattern window to act as a support structure. Alternatively, a soft X-ray mask substrate can be constructed using a thick layer of a first material doped with a small percentage of a second material which expands the first material slightly and on which is deposited a thin layer of the first material such that an etchant may selectively remove enough of the doped first material to create a thin, taut membrane of the undoped first material, transparent to soft X-rays to function as a pattern window, and yet leave sufficient amounts of the doped first material about the pattern window to act as a support structure.
DISCLOSURE OF PREFERRED EMBODIMENT Other objects, features and advantages will occur from the following description of a preferred embodiment and the accompanying drawings in which:
FIG. 1 is an elevational, schematic view of an initial step in the fabrication of a substrate according to this invention for supporting a soft X-ray mask.
FIG. 2 is an elevational schematic view similar to that shown in FIG. 1 of a subsequent step in the fabrication of a soft X-ray mask support substrate according to this invention.
FIG. 3 is an elevational schematic view similar to that of FIG. 2 of a further step in the fabricating of a soft X-ray mask support substrate according to this invention.
FIG. 4 is an elevational schematic view similar to that of FIG. 3 of a completed soft X-ray mask support substrate according to this invention.
FIG. 5 is a elevational, schematic view of an initial step in the fabrication of an alternative substrate according to this invention for supporting a soft X-ray mask.
FIG. 6 is an elevational, schematic view similar to that of FIG. 5 of a subsequent step in the fabrication of FIG. 7 is an elevational, schematic view similar to 1 that of FIG. 6 of a further step in the fabrication of an alternative substrate according to this invention for supporting a soft X-ray mask.
FIG. 8 is an elevational, schematic view similar to that of FIG. 7 of a completed soft X-ray mask support substrate according to this invention.
FIG. 9 is a schematic, axonometric view of a soft X-ray mask support substrate with a plurality of pattern windows and membranes.
In one specific embodiment a support substrate 6 for a soft X-ray mask 8 according to this invention may be constructed, FIG. 1, using a single silicon wafer 10 of the N type or lightly doped P type approximately 200 microns in thickness. Wafer 10 is heavily diffused with boron such that a concentration of about 2 X10" cm exists at a depth of 3 microns from the surface forming boron diffusion layer 12.
Subsequently the wafer 10 is placed in a l 15C solution of 68 ml ethylene diamine, 12g pyrocatechol, and 32 ml water for about 1 15 hours. The solution etches away the bulk of the silicon beneath opening 24 in silicon dioxide layer 14 and creates a pattern window 26, FIG. 4, in the silicon wafer 10 which corresponds to the pattern area 18 which has been created on the opposite side of wafer 10 in the soft X-ray absorbing gold layer 20. This etchant only etches as far as the boron diffused layer 12 and no farther. In addition this etchant also does not attack the chromium or the gold portions. As a result of this etching a membrane 28 is formed from the portion of the boron diffused layer 12 which extends across pattern window 26. Membrane 28 is relatively thin i.e. approximately 3 microns in thickness corresponding in thickness to the boron diffused layer 12. As a result, membrane 28 is quite transparent to the soft X-rays which will be used to expose substrates through pattern area 18 of mask 8.
In addition to providing a support structure which at least in the critical area is sufficiently thin to be relatively transparent to soft X-rays this fabrication technique also introduces a tautness in membrane 28 because of the action of the boron doping in the medium of the silicon: a tension arises because of the slight decrease of the lattice constant produced by boron doping because boron has a smaller covalent bond radius than that of silicon. As a result the membrane 28 shrinks and becomes taut relative to the rest of the silicon substrate which is not doped with boron. Because of this tautness or tension membrane 28 provides a very flat, rigid substrate for the gold absorber layer 20'and its intermediate layer 22; an added advantage of this technique is that the etchant which is used etches much more rapidly in the crystal direction l00 than it does in the direction 1 1 l and so the etching process moves much more quickly in the direction from silicon dioxide layer 14 towards boron diffused layer 12 than it does in the lateral direction transverse to that path so that window 26 is produced in an area beneath opening 24 without any serious undercutting at the sides of window 26 beneath the remaining portions of silicon dioxide layer 14. In fact the etching process provides sloping walls 32 and 34 which slant inwardly in window 26. A mask approximately 1 inch square having 49, 5 um thick pattern windows each 60 mils square has been made with no sagging of the membrane.
Alternatively a support substrate 6 for a soft X-ray mask 8' may be constructed, FIG. 5, using a single crystal silicon wafer 10' approximately 200 microns in thickness. Wafer 10 is heavily diffused with arsenic to a concentration of about 10" atoms/cm.
A three micron epitaxial layer 40, FIG. 6, of pure silicon is grown on one surface and layers 14 and 16' of silicon nitride about one tenth of a micron thick are provided on both surfaces. Silicon nitride layers 14,
16 function to provide a protective layer which prevents undesired chemical attack to the silicon. Following this the desired soft X-ray mask pattern 18', FIG. 7, is fabricated in pattern area 19' of silicon nitride layer 16' using state of the art methods such as scanning electron beam lithograph or photoiithographic techniques. Mask pattern 18' may be formed of gold or any other good soft X-ray absorber. In FIG. 7 a gold layer 20 three tenths of a micron thick is used. Opposite the mask pattern 18' an opening 24' is etched in the silicon nitride layer 14' using an etchant such as concentrated hydrofluoric acid which attacks the silicon nitride layer 14' but not the silicon of wafer Subsequently the wafer 10' is placed in a solution of one part hydrofluoric acid, three parts nitric acid and 10 parts acetic acid for about one and one half hours. This solution etches away the bulk of the arsenic doped silicon beneath opening 24 in silicon nitride layer 14 and creates a pattern window 26, FIG. 8, in the silicon wafer .10 which corresponds to the pattern area 18 which has been created on the opposite side of wafer 10' in the soft X-ray absorbing gold layer 20'. This solution does not attack the gold layer 20', silicon nitride layer 14', 16 or the silicon layer 40. Thus the etching process leaves a membrane 28 formed from the silicon layer 40 which extends across pattern window 26'. Membrane 28' is relatively thin i.e. approximately 3 microns in thicknesscorresponding in thickness to the silicon layer 40. As a result, membrane 28' is quite transparent to the soft X-rays which will be used to expose substrates through pattern area 18' of mask 8'.
In addition to providing a supportstructure which at least in the critical area is sufficiently thin to be relatively transparent to soft X-rays this fabrication technique also introduces a tautness in membrane 28' because of the action of the arsenic doping in the medium of the silicon: a tension arises because of the slight increase of the .lattice constant produced by arsenic doping because arsenic has a largercovalent bond radius than that of silicon. As a result the support structure 30' expands relative to the silicon layer 40 which is not doped with arsenic and causes membrane 28' to become taut. Because of this tautness or tension membrane 28' provides a very flat, rigid substrate for the gold absorber layer 20'.
Typically there are many more than one mask pattern and one pattern window on a substrate. Thus, in FIG. 9, substrate 6" roughly 1 inch square may contain 40 membranes 28" and forty pattern windows 26" each of which is roughly 65 mils square.
Other embodiments will occur to those skilled in the art and are within the following claims:
What is claimed is:
l. A soft X-ray support substrate comprising: a thick silicon peripheral support structure; and a thin, taut, silicon membrane transparent to soft X-rays and carried by said support structure covering the area within the periphery of said support structure for carrying a soft X-ray absorber layer arranged in a predetermined pattern on said membrane within said periphery of said support structure; said membrane being doped with a material having a smaller covalent bond radius than silicon to shrink said membrane to produce tension in it and make it taut.
2. The substrate of claim 1 in which said membrane is formed integrally with said support structure. I
3. The substrate of claim 1 in which said absorber layer includes an absorber element and an intermediate element for improving adherence between said membrane and said absorber element.
4. A soft X-ray support substrate comprising: a thick silicon peripheral support structure; and a thin, taut, silicon membrane transparent to soft X-rays and carried by said support structure covering the area within the periphery of said support structure for carrying a soft X-ray absorber layer arranged in a predetermined pattern on said membrane within said periphery of said support structure; said membrane being doped with boron having a smaller covalent bond radius than silicon to shrink said membrane to produce tension in it and make it taut.
5. A soft X-ray support substrate comprising: a thick silicon peripheral support structure; and a thin, taut, silicon membrane transparent to soft X-rays and carried by said support structure covering the area within the periphery of said support structure for carrying a soft X-ray absorber layer arranged in a predetermined pattern on said membrane within said periphery of said support structure; said membrane being doped with phosphorous having a smaller covalent bond radius than silicon to shrink said membrane to produce tension in it and make it taut.
6. A soft X-ray support substrate comprising: a thick silicon peripheral support structure, and a thin, taut silicon membrane transparent to soft X-rays and carried by said support structure covering the area within the periphery of said support structure for carrying a soft X-ray absorber layer arranged in a predetermined pattern on said membrane within said periphery of said support structure; said support structure being doped with a material having a larger covalent bond radius than silicon to expand said support structure and produce tension in said membrane making it taut.
7. A soft X-ray support substrate comprising: a thick silicon peripheral support structure, and a thin, taut silicon membrane transparent to soft X-rays and carried by said support structure covering the area within the periphery of said support structure for carrying a soft X-ray abosrber layer arranged in a predetermined pattern on said membrane within said periphery of said support structure; said support structure being doped with anitmony having a larger covalent bond radius than silicon to expand said support structure and produce tension in said membrane making it taut.
8. A soft X-ray support substrate comprising: a thick silicon peripheral support structure, and a thin, taut silicon membrane transparent to soft X-rays and carried by said support structure covering the area within the periphery of said support structure for carrying a soft X-ray absorber layer arranged in a predetermined pattern on said membrane within said periphery of said support'structure; said support structure being doped with gallium having a larger covalent bond radius than silicon to expand said support structure and produce tension in said membrane making it taut.
9. A soft X-ray support substrate comprising: a thick silicon peripheral support structure, and a thin, taut silicon membrane transparent to soft X-rays and carried by said support structure covering the area within the periphery of said support structure for carrying a soft X-ray absorber layer arranged in a predetermined pattern on said membrane within said periphery of said support structure; said support structure being doped with arsenic having a larger covalent bond radius than silicon to expand said support structure and produce tension in said membrane making it taut.
10. A soft X-ray support substrate comprising: a thick silicon peripheral support structure, and a thin, taut silicon membrane transparent to soft X-rays and carried by said support structure covering the area within the periphery of said support structure for carrying a soft X-ray absorber layer arranged in a predetermined pattern on said membrane within said periphery of said support structure; said support structure being doped with aluminum having a larger covalent bond radius than silicon to expand said support structure and produce tension in said membrane making it taut.
11. A method of making a soft X-ray mask support substrate comprising: doping a first surface of a silicon substrate with boron toa predetermined thickness to shrink that doped portion of said silicon substrate; providing an etch resistant layer on the second surface of said substrate except in the area corresponding to the area on the first surface for carrying a predetermined pattern in soft X-ray absorber material; and subjecting the exposed said area of said second surface to an etchant which attacks the silicon of the support substrate and which is ineffective in etching the boron doped silicon and the etch resistant layer to create a window in the silicon substrate covered by a membrane formed from the boron doped silicon and kept taut by the shrinking of the boron doped silicon.
12. A method of making a soft X-ray mask support substrate comprising: doping a first surface of a silicon substrate with phosphorous to a predetermined thickness to shrink that doped portion of said silicon substrate; providing an etch resistant layer on the second surface of said substrate except in the area corresponding to the area on the first surface for carrying a predetermined pattern in soft X-ray absorber material; and subjecting the exposed said area of said second surface to an etchant which attacks the silicon of the support substrate and which is ineffective in etching the phosphorous doped silicon and the etch resistant layer to create a window in the silicon substrate covered by a membrane formed from the phosphorous doped silicon and kept taut by the shrinking of the phosphorous doped silicon.
13. A method of making a soft X-ray support substrate comprising:
doping a wafer of silicon with antimony to expand said wafer; depositing a layer of silicon on a first surface of said wafer;
providing an etch resistant layer on the second surface of said wafer except in the area corresponding to the area on the first surface for carrying a predetermined pattern in soft X-ray absorber material; and
subjecting said exposed area of said second surface to an etchant which attacks said silicon wafer doped with antimony and which is ineffective in etching the silicon layer and the etch resistant layer to create a window in the antimony doped siliconwafer covered by a membrane formed from the silicon layer and kept taut by the expansion of the antimony doped silicon wafer. 14. A method of making a soft X-ray support substrate comprising:
doping a wafer of silicon with gallium to expand said wafer;
depositing a layer of silicon on a first surface of said wafer;
providing an etch resistant layer on the second surface of said wafer except in the area corresponding to the area on the first surface for carrying a predetermined pattern in soft X-ray absorber material; and
subjecting said exposed area of said second surface to an etchant which attacks said silicon wafer doped with gallium and which is ineffective in etching the silicon layer and the etch resistant layer to create a window in the gallium doped silicon wafer covered by a membrane formed from the silicon layer and kept taut by the expansion of the gallium doped silicon wafer.
15. A method of making a soft X-ray support substrate comprising:
doping a wafer of silicon with arsenic to expand said wafer;
depositing a layer of silicon on a first surface of said wafer;
providing an etch resistant layer on the second sur face of said wafer except in the area corresponding to the area on the first surface for carrying a predetermined pattern in soft X-ray absorber material; and
subjecting said exposed area of said second surface to an etchant which attacks said silicon wafer doped with arsenic and which is ineffective in etching the silicon layer and the etch resistant layer to create a window in the arsenic doped silicon wafer covered by a membrane formed from the silicon layer and kept taut by the expansion of the arsenic doped silicon wafer.
16. A method of making a soft X-ray support substrate comprising:
doping a wafer of silicon with aluminum to expand said wafer;
depositing a layer of silicon on a first surface of said wafer;
providing an etch resistant layer on the second surface of said wafer except in the area corresponding to the area on the first surface for carrying a predetermined pattern in soft X-ray absorber material; and
subjecting said exposed area of said second surface to an etchant which attacks said silicon wafer doped with aluminum and which is ineffective in etching the silicon layer and the etch resistant layer to create a window in the aluminum doped silicon wafer covered by a membrane formed from the silicon layer and kept taut by the expansion of the aluminum doped silicon wafer.
I i I i
Claims (15)
- 2. The substrate of claim 1 in which said membrane is formed integrally with said support structure.
- 3. The substrate of claim 1 in which said absorber layer includes an absorber element and an intermediate element for improving adherence between said membrane and said absorber element.
- 4. A soft X-ray support substrate comprising: a thick silicon peripheral support structure; and a thin, taut, silicon membrane transparent to soft X-rays and carried by said support structure covering the area within the periphery of said support structure for carrying a soft X-ray absorber layer arranged in a predetermined pattern on said membrane within said periphery of said support structure; said membrane being doped with boron having a smaller covalent bond radius than silicon to shrink said membrane to produce tension in it and make it taut.
- 5. A soft X-ray support substrate comprising: a thick silicon peripheral support structure; and a thin, taut, silicon membrane transparent to soft X-rays and carried by said support structure covering the area within the periphery of said support structure for carrying a soft X-ray absorber layer arranged in a predetermined pattern on said membrane within said periphery of said support structure; said membrane being doped with phosphorous having a smaller covalent bond radius than silicon to shrink said membrane to produce tension in it and make it taut.
- 6. A soft X-ray support substrate comprising: a thick silicon peripheral support structure, and a thin, taut silicon membrane transparent to soft X-rays and carried by said support structure covering the area within the periphery of said support structure for carrying a soft X-ray absorber layer arranged in a predetermined pattern on said membrane within said periphery of said support structure; said support structure being doped with a material having a larger covalent bond radius than silicon to expand said support structure and produce tension in said membrane making it taut.
- 7. A soft X-ray support substrate comprising: a thick silicon peripheral support structure, and a thin, taut silicon membrane transparent to soft X-rays and carried by said support structure covering the area within the periphery of saiD support structure for carrying a soft X-ray abosrber layer arranged in a predetermined pattern on said membrane within said periphery of said support structure; said support structure being doped with anitmony having a larger covalent bond radius than silicon to expand said support structure and produce tension in said membrane making it taut.
- 8. A soft X-ray support substrate comprising: a thick silicon peripheral support structure, and a thin, taut silicon membrane transparent to soft X-rays and carried by said support structure covering the area within the periphery of said support structure for carrying a soft X-ray absorber layer arranged in a predetermined pattern on said membrane within said periphery of said support structure; said support structure being doped with gallium having a larger covalent bond radius than silicon to expand said support structure and produce tension in said membrane making it taut.
- 9. A soft X-ray support substrate comprising: a thick silicon peripheral support structure, and a thin, taut silicon membrane transparent to soft X-rays and carried by said support structure covering the area within the periphery of said support structure for carrying a soft X-ray absorber layer arranged in a predetermined pattern on said membrane within said periphery of said support structure; said support structure being doped with arsenic having a larger covalent bond radius than silicon to expand said support structure and produce tension in said membrane making it taut.
- 10. A soft X-ray support substrate comprising: a thick silicon peripheral support structure, and a thin, taut silicon membrane transparent to soft X-rays and carried by said support structure covering the area within the periphery of said support structure for carrying a soft X-ray absorber layer arranged in a predetermined pattern on said membrane within said periphery of said support structure; said support structure being doped with aluminum having a larger covalent bond radius than silicon to expand said support structure and produce tension in said membrane making it taut.
- 11. A method of making a soft X-ray mask support substrate comprising: doping a first surface of a silicon substrate with boron to a predetermined thickness to shrink that doped portion of said silicon substrate; providing an etch resistant layer on the second surface of said substrate except in the area corresponding to the area on the first surface for carrying a predetermined pattern in soft X-ray absorber material; and subjecting the exposed said area of said second surface to an etchant which attacks the silicon of the support substrate and which is ineffective in etching the boron doped silicon and the etch resistant layer to create a window in the silicon substrate covered by a membrane formed from the boron doped silicon and kept taut by the shrinking of the boron doped silicon.
- 12. A method of making a soft X-ray mask support substrate comprising: doping a first surface of a silicon substrate with phosphorous to a predetermined thickness to shrink that doped portion of said silicon substrate; providing an etch resistant layer on the second surface of said substrate except in the area corresponding to the area on the first surface for carrying a predetermined pattern in soft X-ray absorber material; and subjecting the exposed said area of said second surface to an etchant which attacks the silicon of the support substrate and which is ineffective in etching the phosphorous doped silicon and the etch resistant layer to create a window in the silicon substrate covered by a membrane formed from the phosphorous doped silicon and kept taut by the shrinking of the phosphorous doped silicon.
- 13. A method of making a soft X-ray support substrate comprising: doping a wafer of silicon with antimony to expand said wafer; depositing a layer of silicon on a first surface of said wafer; providing an etch resistant layer on the second surfacE of said wafer except in the area corresponding to the area on the first surface for carrying a predetermined pattern in soft X-ray absorber material; and subjecting said exposed area of said second surface to an etchant which attacks said silicon wafer doped with antimony and which is ineffective in etching the silicon layer and the etch resistant layer to create a window in the antimony doped silicon wafer covered by a membrane formed from the silicon layer and kept taut by the expansion of the antimony doped silicon wafer.
- 14. A method of making a soft X-ray support substrate comprising: doping a wafer of silicon with gallium to expand said wafer; depositing a layer of silicon on a first surface of said wafer; providing an etch resistant layer on the second surface of said wafer except in the area corresponding to the area on the first surface for carrying a predetermined pattern in soft X-ray absorber material; and subjecting said exposed area of said second surface to an etchant which attacks said silicon wafer doped with gallium and which is ineffective in etching the silicon layer and the etch resistant layer to create a window in the gallium doped silicon wafer covered by a membrane formed from the silicon layer and kept taut by the expansion of the gallium doped silicon wafer.
- 15. A method of making a soft X-ray support substrate comprising: doping a wafer of silicon with arsenic to expand said wafer; depositing a layer of silicon on a first surface of said wafer; providing an etch resistant layer on the second surface of said wafer except in the area corresponding to the area on the first surface for carrying a predetermined pattern in soft X-ray absorber material; and subjecting said exposed area of said second surface to an etchant which attacks said silicon wafer doped with arsenic and which is ineffective in etching the silicon layer and the etch resistant layer to create a window in the arsenic doped silicon wafer covered by a membrane formed from the silicon layer and kept taut by the expansion of the arsenic doped silicon wafer.
- 16. A method of making a soft X-ray support substrate comprising: doping a wafer of silicon with aluminum to expand said wafer; depositing a layer of silicon on a first surface of said wafer; providing an etch resistant layer on the second surface of said wafer except in the area corresponding to the area on the first surface for carrying a predetermined pattern in soft X-ray absorber material; and subjecting said exposed area of said second surface to an etchant which attacks said silicon wafer doped with aluminum and which is ineffective in etching the silicon layer and the etch resistant layer to create a window in the aluminum doped silicon wafer covered by a membrane formed from the silicon layer and kept taut by the expansion of the aluminum doped silicon wafer.
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US5570405A (en) * | 1995-06-06 | 1996-10-29 | International Business Machines Corporation | Registration and alignment technique for X-ray mask fabrication |
US6224445B1 (en) | 1996-06-12 | 2001-05-01 | Ait | Actinic radiation source and uses therefor |
US6478974B1 (en) * | 1996-06-24 | 2002-11-12 | The Regents Of The University Of California | Microfabricated filter and shell constructed with a permeable membrane |
WO2004051370A1 (en) * | 2002-12-03 | 2004-06-17 | Dai Nippon Printing Co., Ltd. | Transfer mask blank, transfer mask, and transfer method using the transfer mask |
EP2851749A1 (en) * | 2013-09-23 | 2015-03-25 | National Synchrotron Radiation Research Center | X-ray mask structure and method for preparing the same |
US20160123903A1 (en) * | 2013-03-14 | 2016-05-05 | Pcc Structurals, Inc. | Method of inspecting a part using a marking template for radiography |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3921916A (en) * | 1974-12-31 | 1975-11-25 | Ibm | Nozzles formed in monocrystalline silicon |
JPS5192178A (en) * | 1975-02-10 | 1976-08-12 | ||
JPS5375770A (en) * | 1976-12-17 | 1978-07-05 | Hitachi Ltd | X-ray copying mask |
JPS57211732A (en) * | 1981-06-24 | 1982-12-25 | Toshiba Corp | X ray exposing mask and manufacture thereof |
JPS5944102U (en) * | 1982-05-14 | 1984-03-23 | 株式会社三英社製作所 | High pressure cabinet type switchgear |
DE3338717A1 (en) * | 1983-10-25 | 1985-05-02 | Siemens AG, 1000 Berlin und 8000 München | METHOD FOR PRODUCING A X-RAY MASK WITH METAL CARRIER FILM |
JPH0473765A (en) * | 1990-07-16 | 1992-03-09 | Toshiba Corp | X-ray transmission film and its manufacture |
Citations (1)
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US3637380A (en) * | 1967-06-26 | 1972-01-25 | Teeg Research Inc | Methods for electrochemically making metallic patterns by means of radiation-sensitive elements |
-
1972
- 1972-06-29 US US00267672A patent/US3742230A/en not_active Expired - Lifetime
-
1973
- 1973-06-28 FR FR7323746A patent/FR2202425B1/fr not_active Expired
- 1973-06-28 DE DE2333787A patent/DE2333787C3/en not_active Expired
- 1973-06-28 JP JP7321973A patent/JPS5142469B2/ja not_active Expired
Patent Citations (1)
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US3637380A (en) * | 1967-06-26 | 1972-01-25 | Teeg Research Inc | Methods for electrochemically making metallic patterns by means of radiation-sensitive elements |
Cited By (61)
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US3873824A (en) * | 1973-10-01 | 1975-03-25 | Texas Instruments Inc | X-ray lithography mask |
US3916200A (en) * | 1974-09-04 | 1975-10-28 | Us Energy | Window for radiation detectors and the like |
US3947687A (en) * | 1974-10-23 | 1976-03-30 | The United States Of America As Represented By The Secretary Of The Air Force | Collimated x-ray source for x-ray lithographic system |
US3984680A (en) * | 1975-10-14 | 1976-10-05 | Massachusetts Institute Of Technology | Soft X-ray mask alignment system |
FR2330036A1 (en) * | 1975-10-28 | 1977-05-27 | Hughes Aircraft Co | COVER ABSORBING THE CHARGED PARTICLES AND ITS REALIZATION PROCESS |
US4112307A (en) * | 1976-02-17 | 1978-09-05 | Polymer-Physik Gmbh & Co. Kg | Electron beam source with an electron exit window connected via a window flange |
US4198263A (en) * | 1976-03-30 | 1980-04-15 | Tokyo Shibaura Electric Co., Ltd. | Mask for soft X-rays and method of manufacture |
US4152601A (en) * | 1976-10-19 | 1979-05-01 | Nippon Telegraph & Telephone Public Corporation | X-ray lithography mask and method for manufacturing the same |
US4170512A (en) * | 1977-05-26 | 1979-10-09 | Massachusetts Institute Of Technology | Method of manufacture of a soft-X-ray mask |
US4218503A (en) * | 1977-12-02 | 1980-08-19 | Rockwell International Corporation | X-ray lithographic mask using rare earth and transition element compounds and method of fabrication thereof |
US4215192A (en) * | 1978-01-16 | 1980-07-29 | The Perkin-Elmer Corporation | X-ray lithography apparatus and method of use |
US4342917A (en) * | 1978-01-16 | 1982-08-03 | The Perkin-Elmer Corporation | X-ray lithography apparatus and method of use |
WO1980000634A1 (en) * | 1978-09-13 | 1980-04-03 | Western Electric Co | Radiation mask structure |
US4171489A (en) * | 1978-09-13 | 1979-10-16 | Bell Telephone Laboratories, Incorporated | Radiation mask structure |
US4384919A (en) * | 1978-11-13 | 1983-05-24 | Sperry Corporation | Method of making x-ray masks |
US4536882A (en) * | 1979-01-12 | 1985-08-20 | Rockwell International Corporation | Embedded absorber X-ray mask and method for making same |
US4254174A (en) * | 1979-03-29 | 1981-03-03 | Massachusetts Institute Of Technology | Supported membrane composite structure and its method of manufacture |
US4342817A (en) * | 1979-06-01 | 1982-08-03 | International Business Machines Corporation | Mask for structuring surface areas, and method of making it |
EP0019779A3 (en) * | 1979-06-01 | 1981-10-28 | International Business Machines Corporation | Apertured mask for creating patterned surfaces and process for its manufacture |
EP0019779A2 (en) * | 1979-06-01 | 1980-12-10 | International Business Machines Corporation | Apertured mask for creating patterned surfaces and process for its manufacture |
US4301237A (en) * | 1979-07-12 | 1981-11-17 | Western Electric Co., Inc. | Method for exposing substrates to X-rays |
US4260670A (en) * | 1979-07-12 | 1981-04-07 | Western Electric Company, Inc. | X-ray mask |
US4370556A (en) * | 1979-12-27 | 1983-01-25 | Rudolf Sacher Gesellschaft M.B.H. | Self-supporting mask, method for production as well as use of same |
US4557986A (en) * | 1980-12-17 | 1985-12-10 | Westinghouse Electric Corp. | High resolution lithographic process |
US4454209A (en) * | 1980-12-17 | 1984-06-12 | Westinghouse Electric Corp. | High resolution soft x-ray or ion beam lithographic mask |
US4349621A (en) * | 1981-04-13 | 1982-09-14 | General Electric Company | Process for X-ray microlithography using thin film eutectic masks |
US4468799A (en) * | 1981-05-18 | 1984-08-28 | U.S. Philips Corporation | Radiation lithography mask and method of manufacturing same |
JPH0319690B2 (en) * | 1981-05-18 | 1991-03-15 | Fuiritsupusu Furuuiranpenfuaburiken Nv | |
JPS57198461A (en) * | 1981-05-18 | 1982-12-06 | Philips Nv | Radiant lithographic mask and manufacture thereof |
US4477921A (en) * | 1981-11-27 | 1984-10-16 | Spire Corporation | X-Ray lithography source tube |
US4555460A (en) * | 1982-09-01 | 1985-11-26 | U.S. Philips Corporation | Mask for the formation of patterns in lacquer layers by means of X-ray lithography and method of manufacturing same |
US4468282A (en) * | 1982-11-22 | 1984-08-28 | Hewlett-Packard Company | Method of making an electron beam window |
US4576832A (en) * | 1982-12-30 | 1986-03-18 | International Business Machines Corporation | Self-aligning mask |
EP0167948A3 (en) * | 1984-07-07 | 1986-07-16 | Licentia Patent-Verwaltungs-Gmbh | X-ray mask |
US4647517A (en) * | 1984-07-07 | 1987-03-03 | Licentia Patent-Verwaltungs-Gmbh | Mask for X-ray lithography |
EP0167948A2 (en) * | 1984-07-07 | 1986-01-15 | Licentia Patent-Verwaltungs-GmbH | X-ray mask |
US4708919A (en) * | 1985-08-02 | 1987-11-24 | Micronix Corporation | Process for manufacturing a mask for use in X-ray photolithography using a monolithic support and resulting structure |
JPH0658874B2 (en) * | 1986-03-18 | 1994-08-03 | 富士通株式会社 | X-ray mask manufacturing method |
JPS62216325A (en) * | 1986-03-18 | 1987-09-22 | Fujitsu Ltd | Manufacture of x-ray mask |
US4855197A (en) * | 1986-05-06 | 1989-08-08 | International Business Machines Corporation | Mask for ion, electron or X-ray lithography and method of making it |
US5115456A (en) * | 1988-12-23 | 1992-05-19 | Hitachi, Ltd. | Mask for exposing wafer with radiation and its exposing method |
US5096791A (en) * | 1988-12-30 | 1992-03-17 | Technion Research And Development Foundation, Ltd. | Method for preparation of mask for x-ray lithography |
US5146481A (en) * | 1991-06-25 | 1992-09-08 | Diwakar Garg | Diamond membranes for X-ray lithography |
EP0542265A1 (en) * | 1991-11-15 | 1993-05-19 | Canon Kabushiki Kaisha | X-ray mask structure and x-ray exposing method, and semiconductor device manufactured by use of x-ray mask structure, and method for manufacturing x-ray mask structure |
US5422921A (en) * | 1991-11-15 | 1995-06-06 | Canon Kabushiki Kaisha | X-ray mask structure and manufacturing methods including forming a metal oxide film on a portion of an X-ray permeable film having no X-ray absorber thereon |
US5529862A (en) * | 1993-09-01 | 1996-06-25 | Texas Instruments Incorporated | Method of forming a low distortion stencil mask |
US5763121A (en) * | 1993-09-01 | 1998-06-09 | Texas Instruments Incorporated | Low distortion stencil mask |
US5491331A (en) * | 1994-04-25 | 1996-02-13 | Pilot Industries, Inc. | Soft x-ray imaging device |
US5504324A (en) * | 1994-04-25 | 1996-04-02 | Pilot Industries, Inc. | Soft x-ray imaging device employing a cylindrical compression spring to maintain the position of a microchannel plate |
US5570405A (en) * | 1995-06-06 | 1996-10-29 | International Business Machines Corporation | Registration and alignment technique for X-ray mask fabrication |
US6224445B1 (en) | 1996-06-12 | 2001-05-01 | Ait | Actinic radiation source and uses therefor |
US6478974B1 (en) * | 1996-06-24 | 2002-11-12 | The Regents Of The University Of California | Microfabricated filter and shell constructed with a permeable membrane |
US7582393B2 (en) | 2002-12-03 | 2009-09-01 | Dai Nippon Printing Co., Ltd. | Transfer mask blank, transfer mask, and transfer method using the transfer mask |
US20060068298A1 (en) * | 2002-12-03 | 2006-03-30 | Hisatake Sano | Transfer mask blank, transfer mask, and transfer method using the transfer mask |
WO2004051370A1 (en) * | 2002-12-03 | 2004-06-17 | Dai Nippon Printing Co., Ltd. | Transfer mask blank, transfer mask, and transfer method using the transfer mask |
US20160123903A1 (en) * | 2013-03-14 | 2016-05-05 | Pcc Structurals, Inc. | Method of inspecting a part using a marking template for radiography |
US9658172B2 (en) * | 2013-03-14 | 2017-05-23 | Pcc Structurals | Method of inspecting a part using a marking template for radiography |
EP2851749A1 (en) * | 2013-09-23 | 2015-03-25 | National Synchrotron Radiation Research Center | X-ray mask structure and method for preparing the same |
CN104460222A (en) * | 2013-09-23 | 2015-03-25 | 许博渊 | X-ray mask structure and method for preparing the same |
US20150085974A1 (en) * | 2013-09-23 | 2015-03-26 | National Synchrotron Radiation Research Center | X-ray mask structure and method for preparing the same |
US9152036B2 (en) * | 2013-09-23 | 2015-10-06 | National Synchrotron Radiation Research Center | X-ray mask structure and method for preparing the same |
Also Published As
Publication number | Publication date |
---|---|
FR2202425B1 (en) | 1976-05-28 |
DE2333787C3 (en) | 1978-06-15 |
FR2202425A1 (en) | 1974-05-03 |
DE2333787A1 (en) | 1974-01-17 |
JPS5142469B2 (en) | 1976-11-16 |
DE2333787B2 (en) | 1977-10-20 |
JPS4959575A (en) | 1974-06-10 |
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