CA1165761A - Class of e-beam resists based on conducting organic charge transfer salts - Google Patents
Class of e-beam resists based on conducting organic charge transfer saltsInfo
- Publication number
- CA1165761A CA1165761A CA000354062A CA354062A CA1165761A CA 1165761 A CA1165761 A CA 1165761A CA 000354062 A CA000354062 A CA 000354062A CA 354062 A CA354062 A CA 354062A CA 1165761 A CA1165761 A CA 1165761A
- Authority
- CA
- Canada
- Prior art keywords
- charge transfer
- transfer material
- organic charge
- conducting organic
- halogen salt
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 238000012546 transfer Methods 0.000 title claims abstract description 82
- 150000003839 salts Chemical class 0.000 title abstract description 13
- 239000000463 material Substances 0.000 claims abstract description 91
- 238000000034 method Methods 0.000 claims abstract description 48
- 229920002120 photoresistant polymer Polymers 0.000 claims abstract description 8
- 229910052736 halogen Inorganic materials 0.000 claims description 82
- -1 halogen salts Chemical class 0.000 claims description 77
- 238000010894 electron beam technology Methods 0.000 claims description 20
- FHCPAXDKURNIOZ-UHFFFAOYSA-N tetrathiafulvalene Chemical compound S1C=CSC1=C1SC=CS1 FHCPAXDKURNIOZ-UHFFFAOYSA-N 0.000 claims description 13
- 150000002367 halogens Chemical class 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 10
- UFPVYWYEZPMUQL-UHFFFAOYSA-N 2-(1,3-diselenol-2-ylidene)-1,3-diselenole Chemical compound [Se]1C=C[Se]C1=C1[Se]C=C[Se]1 UFPVYWYEZPMUQL-UHFFFAOYSA-N 0.000 claims description 7
- CJVYYDCBKKKIPD-UHFFFAOYSA-N 1-n,1-n,2-n,2-n-tetramethylbenzene-1,2-diamine Chemical class CN(C)C1=CC=CC=C1N(C)C CJVYYDCBKKKIPD-UHFFFAOYSA-N 0.000 claims description 6
- WJWOFBKLBKILJV-UHFFFAOYSA-N 1,2,3,4-benzotetrathiine Chemical compound S1SSSC2=CC=CC=C21 WJWOFBKLBKILJV-UHFFFAOYSA-N 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 229910052794 bromium Inorganic materials 0.000 claims description 4
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 claims description 4
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 claims description 4
- 150000004032 porphyrins Chemical class 0.000 claims description 4
- JIWVFTDJMANAGG-FPLPWBNLSA-N (2z)-4-methyl-2-(4-methyl-1,3-diselenol-2-ylidene)-1,3-diselenole Chemical compound [Se]1C(C)=C[Se]\C1=C/1[Se]C(C)=C[Se]\1 JIWVFTDJMANAGG-FPLPWBNLSA-N 0.000 claims description 3
- BTQDPOVTMFCMKB-UHFFFAOYSA-N 2-(1,3-dithiol-2-ylidene)-4,5-dimethyl-1,3-dithiole Chemical compound S1C(C)=C(C)SC1=C1SC=CS1 BTQDPOVTMFCMKB-UHFFFAOYSA-N 0.000 claims description 3
- YMWLPMGFZYFLRP-UHFFFAOYSA-N 2-(4,5-dimethyl-1,3-diselenol-2-ylidene)-4,5-dimethyl-1,3-diselenole Chemical compound [Se]1C(C)=C(C)[Se]C1=C1[Se]C(C)=C(C)[Se]1 YMWLPMGFZYFLRP-UHFFFAOYSA-N 0.000 claims description 3
- HGOTVGUTJPNVDR-UHFFFAOYSA-N 2-(4,5-dimethyl-1,3-dithiol-2-ylidene)-4,5-dimethyl-1,3-dithiole Chemical compound S1C(C)=C(C)SC1=C1SC(C)=C(C)S1 HGOTVGUTJPNVDR-UHFFFAOYSA-N 0.000 claims description 3
- VRSXBMGXAHSMFB-UHFFFAOYSA-N 2-(5,6-dihydro-4h-cyclopenta[d][1,3]diselenol-2-ylidene)-5,6-dihydro-4h-cyclopenta[d][1,3]diselenole Chemical compound C1CCC([Se]2)=C1[Se]C2=C([Se]1)[Se]C2=C1CCC2 VRSXBMGXAHSMFB-UHFFFAOYSA-N 0.000 claims description 3
- DTJPUCUJANTIIU-UHFFFAOYSA-N 2-(5,6-dihydro-4h-cyclopenta[d][1,3]dithiol-2-ylidene)-5,6-dihydro-4h-cyclopenta[d][1,3]dithiole Chemical compound C1CCC(S2)=C1SC2=C(S1)SC2=C1CCC2 DTJPUCUJANTIIU-UHFFFAOYSA-N 0.000 claims description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 3
- WDEQGLDWZMIMJM-UHFFFAOYSA-N benzyl 4-hydroxy-2-(hydroxymethyl)pyrrolidine-1-carboxylate Chemical compound OCC1CC(O)CN1C(=O)OCC1=CC=CC=C1 WDEQGLDWZMIMJM-UHFFFAOYSA-N 0.000 claims description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- 239000000460 chlorine Substances 0.000 claims description 3
- 238000004132 cross linking Methods 0.000 claims description 3
- RBTKNAXYKSUFRK-UHFFFAOYSA-N heliogen blue Chemical compound [Cu].[N-]1C2=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=NC([N-]1)=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=N2 RBTKNAXYKSUFRK-UHFFFAOYSA-N 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 239000000758 substrate Substances 0.000 claims description 3
- FSBQGCIXVCZLAE-UHFFFAOYSA-N CN1C(C(C)=C2C3=CC=CC=C3C(C(C)=C3C4=CC=CC=C4C(=C4C)N3C)=N2)=C(C=CC=C2)C2=C1C(C)=C1C2=C(C)C(C)=CC=C2C4=N1 Chemical class CN1C(C(C)=C2C3=CC=CC=C3C(C(C)=C3C4=CC=CC=C4C(=C4C)N3C)=N2)=C(C=CC=C2)C2=C1C(C)=C1C2=C(C)C(C)=CC=C2C4=N1 FSBQGCIXVCZLAE-UHFFFAOYSA-N 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- MPMSMUBQXQALQI-UHFFFAOYSA-N cobalt phthalocyanine Chemical compound [Co+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 MPMSMUBQXQALQI-UHFFFAOYSA-N 0.000 claims description 2
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims description 2
- 229910052740 iodine Inorganic materials 0.000 claims description 2
- MHWBQGKJIQGLDP-UHFFFAOYSA-N 3,4,5,6-tetramethyldiselenine Chemical compound CC1=C(C(=C([Se][Se]1)C)C)C MHWBQGKJIQGLDP-UHFFFAOYSA-N 0.000 claims 3
- YHYJVKOUVFXEON-UHFFFAOYSA-N 3,4,5,6-tetraphenyldiselenine Chemical compound C1(=CC=CC=C1)C1=C(C(=C([Se][Se]1)C1=CC=CC=C1)C1=CC=CC=C1)C1=CC=CC=C1 YHYJVKOUVFXEON-UHFFFAOYSA-N 0.000 claims 3
- KMHSUNDEGHRBNV-UHFFFAOYSA-N 2,4-dichloropyrimidine-5-carbonitrile Chemical compound ClC1=NC=C(C#N)C(Cl)=N1 KMHSUNDEGHRBNV-UHFFFAOYSA-N 0.000 claims 2
- JKPYOWXCHRIGII-UHFFFAOYSA-N [Ni].CN1C(C(C)=C2C3=CC=CC=C3C(C(C)=C3C4=CC=CC=C4C(=C4C)N3C)=N2)=C(C=CC=C2)C2=C1C(C)=C1C2=C(C)C(C)=CC=C2C4=N1 Chemical class [Ni].CN1C(C(C)=C2C3=CC=CC=C3C(C(C)=C3C4=CC=CC=C4C(=C4C)N3C)=N2)=C(C=CC=C2)C2=C1C(C)=C1C2=C(C)C(C)=CC=C2C4=N1 JKPYOWXCHRIGII-UHFFFAOYSA-N 0.000 claims 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims 1
- SYKNUAWMBRIEKB-UHFFFAOYSA-N [Cl].[Br] Chemical compound [Cl].[Br] SYKNUAWMBRIEKB-UHFFFAOYSA-N 0.000 claims 1
- 239000010941 cobalt Substances 0.000 claims 1
- 229910017052 cobalt Inorganic materials 0.000 claims 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims 1
- 239000011630 iodine Substances 0.000 claims 1
- 230000003287 optical effect Effects 0.000 abstract description 14
- 230000008569 process Effects 0.000 abstract description 4
- 238000000859 sublimation Methods 0.000 abstract description 4
- 230000008022 sublimation Effects 0.000 abstract description 4
- 238000007614 solvation Methods 0.000 abstract 1
- 238000000807 solvent casting Methods 0.000 abstract 1
- 239000010408 film Substances 0.000 description 46
- 238000010521 absorption reaction Methods 0.000 description 7
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- 238000011161 development Methods 0.000 description 6
- 230000018109 developmental process Effects 0.000 description 6
- 230000009102 absorption Effects 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 230000005855 radiation Effects 0.000 description 4
- 230000035945 sensitivity Effects 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 230000001419 dependent effect Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 230000003068 static effect Effects 0.000 description 3
- 238000009835 boiling Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002798 polar solvent Substances 0.000 description 2
- 230000007261 regionalization Effects 0.000 description 2
- 238000012552 review Methods 0.000 description 2
- 239000011669 selenium Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 238000006276 transfer reaction Methods 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 1
- 230000001464 adherent effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 238000006664 bond formation reaction Methods 0.000 description 1
- 238000012668 chain scission Methods 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000609 electron-beam lithography Methods 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 238000010849 ion bombardment Methods 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012454 non-polar solvent Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000000206 photolithography Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 150000003342 selenium Chemical class 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
-
- 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
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
-
- 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
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
Landscapes
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- General Physics & Mathematics (AREA)
- Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)
- Photoreceptors In Electrophotography (AREA)
- Electron Beam Exposure (AREA)
Abstract
ABSTRACT
Novel E-beam resists and process for their use are described. These resists are conducting organic charge transfer salts. Films of these materials can be deposited by solvent casting or by sublimation.
The deposited film can be made to produce a positive or negative resist image depending on the E-beam energy and exposure time. Exposure of this material to an E-beam produces patterns having differential electrical, optical and solvation properties.
Novel E-beam resists and process for their use are described. These resists are conducting organic charge transfer salts. Films of these materials can be deposited by solvent casting or by sublimation.
The deposited film can be made to produce a positive or negative resist image depending on the E-beam energy and exposure time. Exposure of this material to an E-beam produces patterns having differential electrical, optical and solvation properties.
Description
7~1 NEW CLASS OF E-BEAM RESISTS BASED OW
CONDUCTING ORGANIC CHARGE TRANSFER SALTS
BACKGROUND OF THE INVENTION
Field of the Invention The invention lies in the field of electron beam resist compositions and the production of patterned thin film layers thereof.
Prior Art The prior art is replete with radiation sensitive materials as resis~ts and with their use in pattern formation in the fabrication of microelectronic devices. In the prior art, pattern formation in these materials is dependent upon dif~erential solubility between irradiated and unirradiated regions. These solubility changes are produced by either bondbreaking, (chain scission) or bond formation (chain crosslinking) in polymeric systems. This occurs in the presence of actinic radiation, E-beam radiation or X-ray radiation.
The prior art materials have several drawbacks among which is the difficulty of obtaining sharp Yos7s-07s 1 ~6~7~ 1 images of high resolution, particularly in negative resists. This is due to the swelling of the polymeric material during solvent development.
Films or prior art materials are generally insulative in nature and as such tend to buildup static charges on their surfaces during irradiation. In the prior art this problem is overcome by the deposition of a thin metal film on top of the polymeric resist material. In addition it is dif~icult to produce films of uniform thickness by solvent coating techniques on surfaces ~ith topography.
The state of the art in electron-beam lithography can be readily reviewed in a review entitled "CRC Critical Reviews" by M. J. Bowden, Solid State and Material 5ciences, 8, 223 (1979).
SUMMARY OF THE INVENTION
What has been discovered here are novel electron-beam resists which can be broadly classified as conducting organic charge transfer salts. More 2d specifically, the materials can be selected from the halogen salts of tetrathiafulvalene (TTF) and its derivatives, its selenium analog tetraselenafulvalene (TSeF) and its derivatives, tetraheterotetracenes, tetramethylphenylenediamines, phthalocyanines, porphyrins and derivatives of these ~-donors. The halogen can be selected from iodine, bromine and chlorine.
In another embodiment there is described a method for providing a positive resist image using a film of one of the above compounds.
In yet another embodiment a method for providing a negative resist image is provided.
D~SCRIPT~ON OF THE INVENTION
The present invention teaches novel electron-beam resist materi~ls which can be used to provide either a positive or negative resist image depending upon irradiation energy parameters. Principally, the materials can be selected from several classes of conducting organic ~-donor complexes. For example, they can be selected from tetraheterofulvalenes and derivatives thereof having the general structural formula where X is S and/or Se, R ~ X ~ X~ R CH8, C2H5 tetraheterotetracenes and derivatives thereof having the general structural formula ~ where X is S and/or Se:
tetraheteronaphthalene and derivatives thereof having the general structural formula where X is S and/or Se:
X--X
~ :~657~i ]
perylene and derivatives thereof having the general structural formula r ~'1 biheteropyrans and derivatives thereof having the general structural formula R ~ R where X is S and or Se, X ~ X or N-alkyl and R is ~ ~ alkyl, phenyl R R
tetramethylphenylenediamine and derivatives thereof having the general structural formula CH3~ ~ ,CH3 phthalocyanines and derivatives thereof having the general structural formula f ~ where M is a transition ~N N~ metal, e.g., Ni, Cu, Fe, N~ ~N ~ Co, Pt, and the like ~N~
~ 16S7~ 1 and porphyrins and derivatives thereof having the general structural formula where ~ is a transition ~_ ~/ N- - ~ i metal ~e ~ c Y~
The above ~-donor compositlons form conducting charge transfer compositions in the presence of a halogen according to the following equation:
~-Donor + X2 ~ Donor)l_n (~-Donor )n (X )n o<n<l X can be Cl, Br or I.
It is well known that to achieve high conductivity the stoichiometry (i.e. n in the above equation) of the charge transfer salt must be less than one. Also, the value of n can be usually varied over a range of values between 0 and 1 without significantly chan~ing the conducting properties.
The above ~-donors have been found to be the basis of a new lithographic process. Th-s process is based on the discovery that exposure of the charge transfer salt to an electron beam having sufficient current density causes the loss of the halogen in the charge transfer salt where it is irradiated. That is, the electron-beam causes a reverse charge transfer reaction to occur as in the following equation:
(D or) (~-Donor+)n(X )n lrradlation In general these charge transfer salts can be deposited ~ 16i)7fi 1 ~y sublimation. They give smooth, adherent and glass-like films. Films having uniform thickness in the range of about 3000 angstroms to about
CONDUCTING ORGANIC CHARGE TRANSFER SALTS
BACKGROUND OF THE INVENTION
Field of the Invention The invention lies in the field of electron beam resist compositions and the production of patterned thin film layers thereof.
Prior Art The prior art is replete with radiation sensitive materials as resis~ts and with their use in pattern formation in the fabrication of microelectronic devices. In the prior art, pattern formation in these materials is dependent upon dif~erential solubility between irradiated and unirradiated regions. These solubility changes are produced by either bondbreaking, (chain scission) or bond formation (chain crosslinking) in polymeric systems. This occurs in the presence of actinic radiation, E-beam radiation or X-ray radiation.
The prior art materials have several drawbacks among which is the difficulty of obtaining sharp Yos7s-07s 1 ~6~7~ 1 images of high resolution, particularly in negative resists. This is due to the swelling of the polymeric material during solvent development.
Films or prior art materials are generally insulative in nature and as such tend to buildup static charges on their surfaces during irradiation. In the prior art this problem is overcome by the deposition of a thin metal film on top of the polymeric resist material. In addition it is dif~icult to produce films of uniform thickness by solvent coating techniques on surfaces ~ith topography.
The state of the art in electron-beam lithography can be readily reviewed in a review entitled "CRC Critical Reviews" by M. J. Bowden, Solid State and Material 5ciences, 8, 223 (1979).
SUMMARY OF THE INVENTION
What has been discovered here are novel electron-beam resists which can be broadly classified as conducting organic charge transfer salts. More 2d specifically, the materials can be selected from the halogen salts of tetrathiafulvalene (TTF) and its derivatives, its selenium analog tetraselenafulvalene (TSeF) and its derivatives, tetraheterotetracenes, tetramethylphenylenediamines, phthalocyanines, porphyrins and derivatives of these ~-donors. The halogen can be selected from iodine, bromine and chlorine.
In another embodiment there is described a method for providing a positive resist image using a film of one of the above compounds.
In yet another embodiment a method for providing a negative resist image is provided.
D~SCRIPT~ON OF THE INVENTION
The present invention teaches novel electron-beam resist materi~ls which can be used to provide either a positive or negative resist image depending upon irradiation energy parameters. Principally, the materials can be selected from several classes of conducting organic ~-donor complexes. For example, they can be selected from tetraheterofulvalenes and derivatives thereof having the general structural formula where X is S and/or Se, R ~ X ~ X~ R CH8, C2H5 tetraheterotetracenes and derivatives thereof having the general structural formula ~ where X is S and/or Se:
tetraheteronaphthalene and derivatives thereof having the general structural formula where X is S and/or Se:
X--X
~ :~657~i ]
perylene and derivatives thereof having the general structural formula r ~'1 biheteropyrans and derivatives thereof having the general structural formula R ~ R where X is S and or Se, X ~ X or N-alkyl and R is ~ ~ alkyl, phenyl R R
tetramethylphenylenediamine and derivatives thereof having the general structural formula CH3~ ~ ,CH3 phthalocyanines and derivatives thereof having the general structural formula f ~ where M is a transition ~N N~ metal, e.g., Ni, Cu, Fe, N~ ~N ~ Co, Pt, and the like ~N~
~ 16S7~ 1 and porphyrins and derivatives thereof having the general structural formula where ~ is a transition ~_ ~/ N- - ~ i metal ~e ~ c Y~
The above ~-donor compositlons form conducting charge transfer compositions in the presence of a halogen according to the following equation:
~-Donor + X2 ~ Donor)l_n (~-Donor )n (X )n o<n<l X can be Cl, Br or I.
It is well known that to achieve high conductivity the stoichiometry (i.e. n in the above equation) of the charge transfer salt must be less than one. Also, the value of n can be usually varied over a range of values between 0 and 1 without significantly chan~ing the conducting properties.
The above ~-donors have been found to be the basis of a new lithographic process. Th-s process is based on the discovery that exposure of the charge transfer salt to an electron beam having sufficient current density causes the loss of the halogen in the charge transfer salt where it is irradiated. That is, the electron-beam causes a reverse charge transfer reaction to occur as in the following equation:
(D or) (~-Donor+)n(X )n lrradlation In general these charge transfer salts can be deposited ~ 16i)7fi 1 ~y sublimation. They give smooth, adherent and glass-like films. Films having uniform thickness in the range of about 3000 angstroms to about
2 microns or more have been depositedO In cases where the salt has a low vapor pressure or is thermally unstable, films can be formed by solution coating techniques.
It was further discovered here that these materials can be made to provide either negative or positive resist images. The imaging mode depends upon the parameters of the electron-beam, e.g., its energy, and charge density. For example, in the case for negative images, the electron-beam is in a range of from about 5KeV to about 30XeV. The charge density is at least in the 10 4 to 10 3c/cm2 range.
The exposure is performed at room temperature. The images are developed in suitable polar solvents such as short chain alcohols, water, dimethylformamide, dimethylsulfoxide, acetonitrile and the like.
The negative image undergoes crosslinking and gives desirable patterns which are unchanged in hot solvents.
For example, when a negative image was formed on a film of tetrathiafulvalene bromide the image was subjected to boiling chlorobenzene, dimethylsulfoxide and the like without change. The imase was also subjected to temperatures of 275C in vacuum at 10 6 torr and again without change. These images undergo lift-off readily when treated with aqueous hydrazine for about 1-2 minutes at room temperature.
Negative resist images having dimensions of less than 1 micron, with excellent edge definition of about 0.1 micron, and near vertical walls have been obtained.
No swelling occurred in the images when washed in a wide variety of polar and non-polar solvents.
7 ~l6~7~l Positive resist images can be prepared either in situ or by solvent development. In the in situ rnode the resist is exposed to electron-beam radiatio~ having charge density in the 10 3to 10 1 coul/cm2 range and 5 an energy of from about 5KeV to about 30KeV. At these charge densities levels the exposed resist materials are caused to sublime. This sublimation can be enhanced by heating the substrate upon which the resist lies to temperatures in the range of about 60C to about 100C.
Solvent developed positive images are obtained in those instances where the charge transfer salts do not readily crosslink upon exposure after halogen loss. That halogen loss is effected upon exposure is ascertained by electron microprobe techniques. The exposed materials are readily removed with low polarity solvents such as methylene chloride, chlorform, carbon tetrachloride and the like. The advantage of the solvent development is that in principle more sensitive positive resists can be obtained. An additional feature of solvent development is that less volatile donors used in the image coating process.
Another discovery of the invention disclosed is the different electrical and optical proper~ies ~etween exposed and unexposed materials of the invention.
It was known that the unexposed films were highly conductive having conductivities in the range of from about 0.1 to about 20/ohm-cm. This conductivity i~ of practical advantage because it elminates static charge build up in the film during irradiation.
With prior insulating polymer resists, this problem required that a thin metal layer be deposited on the resi~t. With the present materials this requirement no longer exist. While the unexposed resist exhibits conductivity, the exposed resist is .
1 ~6~7~ 1 found to be insulating. For example, when a film of tetrathiafulvalene bromide is sublimed onto a substrate and its conductivity measured, and compared with the conductivity of the developed electron-beam negative image, it was found that there was change in conductivity of over 8 orders of magnitude. The unexposed resist exhibited a conductivity of 20/ohm-cm, while the exposed regions exhibited a conductivity of less than 10 7/ohm-cm.
It has also been observed that large optical property changes occur in the exposed part of the resist. It is observed that the unexposed resist films strongly absorb light in the visible and near infrared, while the exposed films are non-absorbing in these regions. For example, it is found that films of tetrathiafulvalene bromide have strong absorptions at 5500A and at 3800A. After irra~iation, optical measurements disclosed that these absorptions were absent in the exposed regions. It should be noted that development is not necessary to optically detect electron-beam written patterns on the subject films.
Optical absorption is, of course, dependent upon composition. For example, charge transfer salts such as tetrathiatetracene and tetraphenyl dithiopyran are strongly O O
absorbing in the 8000A to 8500A region. This light absorbing difference in unexposed versus exposed materials lend applications to optical masks and in video storage devices.
The sensitivity of the lithographic process as well as the optical and electrical properties of the present resists are dependent upon respective halogen content and the electron-beam parameters.
Improvement in the sensitivity of the reverse charge ~ 1~S76 1 transfer reaction have been seen in going from tetrathiafulvalene bromide to the chloride salt. This improved the sensitivity by over a factor of 5. In another example, a film of the neutral donor is deposited and then treated with halogen transfer salt with a smaller molar content of halogen. Electron-beam irradiation of this material therefor has to remove less halogen and leads to corresponding enhancement in sensitivity.
The following examples are by way of illustration and not by way of limitation.
Example 1 A film of tetrathiafulvalene bromide of (TTF-Brn) about 5000A thick is prepared by vacuum subliming TTF-Brn at a pressure of 1 micron and a temperature of 185C to about 190C. Sublimation is continued for about 10 minutes.
Analysis of the thus produced film shows a non-stoichrometric composition of TTF-BrO 78.
An image is formed on the film by impinging an electron-beam thereon in a predetermined pattern. The electron-beam had a current density of about 10 4 coulomb/cm2 and an energy of lOKeV. The film is then washed with methanol for about 15 seconds at room temperature to remove the unexposed areas of the film. A negative resist image remained having dimensions less than 1 micron.
The image is unchanged after boiling in chlorobenzene or dimethylsulfoxide and on heating to 275C in vacuum. It is removed however, when it is washed with aqueous hydrazine for about 1-2 minutes at room temperature.
Optical absorption as well as conductivity measurements were made on the film prior and subsequent to exposure. Prior to exposure the film dlsclosed the characteristic TTF-Br salt absorptions at 5500A and 3800A. After exposure these absorptions were absent. Similarly, the conductivity of the film was 20/ohm-cm prior to exposure and was found to be less than 10 7/ohm-cm subsequently.
Example 2 A film of TTF-BrO 78 is prepared as in Example 1. The film is irradiated in a predetermined pattern with a electron-beam having a current density of about 10 3 coulomb/cm and an energy of 10KeV. After irradiation it is found that the exposed film is removed leaving a positive resist image. The image exhibited dimensions of less than one micron with near vertical walls. Further development is not required.
Bxample 3 A film of tetrathiafulvalene chloride (TTF-Clo 65) is prepared as in Example 1 except that a bath temperature of 195C to 205C is used. The stoichiometry of the film is found to be TTF-Clo 65. The film is irradiated and subsequently treated as in Example 1 to effect a negative image. It is found that the solubility, optical and electrical properties are similar to the film deposited in Example 1. It is further found that the TTF-Clo 65 proves to be about 5 times more sensitive that the TTF-BrO 78 film of Example 1.
- ' S 7 ~ t Example 4 A film of TTF-Clo 65 is prepared as in Example 3 and is irradiated and treated as in Example 2. A positlve resist image obtained without solvent developr.lent.
The image has dimensions of less than 1 micron with almost vertical walls.
Example 5 A film of tetrathiafulvalene iodide (TTF-In) is prepared by the procedure disclosed in Example 1 except that a heating temperature of about 140C to about 150C is used. ~nalysis of the film discloses a stoichiometry of TTF-Io 7. The film is irradiated and subsequently treated as the analogous films of Examples 1 and 2 to produce both negative and positive resist images respectively. The solubility, optical and electrical properties are very similar to the films produced in Examples 1 and 2.
Example 6 A film of tetraselenafulvalene bromide (TSeF-Brn) is prepared as in Example 1 to give a film composition of TSeF-BrO 8. This film is irradiated and subsequently treated as in Examples 1 and 2 to give both negative and positive resist images respectively. Optical measurements discloses that the unexposed film have strong absorptions at 43002 and 6500~. Similar changes in solubility, optical and electrical properties as disclosed in Example 1 are observed.
Example 7 Tetrathiatetracene (TTT) is sublimed in vacuum at 1 micron and 350C to give a neutral TTT film. The film is then exposed to bromine vapor for about 10 12 ~1~57fit mins. to provide a conducting film having a stoichiometry of TTT-BrO 1 The film is irradiated and treated in the r,lanner given in Examples 1 and 2 to obtain negative and positive resist images ~hich exhibit similar electrical changes as in the previous Examples.
Halogen salts of the following materials similarly can be used as electron-beam resist and treated in a manner similar to that disclosed in the above examples.
diselenadithiafulvalene dimethyltetrathiafulvalene dimethyltetraselenafulvalene dimethyldiselenadithiafulvalene tetramethyltetrathiafulvalene tetramethyltetraselenafulvalene tetramethyldiselenadithiafulvalene hexamethylenetetrathiafulvalene hexamethylenetetraselenafulvalene hexamethylenediselenadithiafulvalene tetrathianaphthalene tetraselenaphthalene tetrathianaphthalene tetraselenanaphthalene perylene dithiopyran tetramethyldithiopyran tetraphenyldithiopyran diselenapyran tetramethyldiselenapyran tetraphenyldiselenapyran dipyran tetramethylphenylenediamine phthalocyanine nickel phthalocyanine copper phthalocyanine cobalt phthalocyanine 1 1 6 ~ 7~ ~
iron phthalocyanine octamethyltetrabenzporphyrins nic~el octamethyltetrabenzporphyrins The above listing of materials is not meant to indicate that the scope of the invention should be limited thereby. One skilled in the art would know the list not to be exhaustive but that many other compounds derived fro~ those listed above and throughout the specification can also be used in the furtherance of the present invention.
The invention hereinabove described includes a novel class of resist materials which can be generally classified as conducting organic charge transfer salts. These materials can give rise to both negative and positive resists merely by controlling the irradiation parameters, i.e., energy and current density. The resists have other advantages including large changes in solubility, optical and electrical properties which result upon irradiation. These properties lead to their usefulness in the ~abrication of microstructures for large scale integration of electronic circuits, as optical storage media, for fabricating master masks used in photolithography and in eliminating static charging in the resist during electron or ion bombardment.
It was further discovered here that these materials can be made to provide either negative or positive resist images. The imaging mode depends upon the parameters of the electron-beam, e.g., its energy, and charge density. For example, in the case for negative images, the electron-beam is in a range of from about 5KeV to about 30XeV. The charge density is at least in the 10 4 to 10 3c/cm2 range.
The exposure is performed at room temperature. The images are developed in suitable polar solvents such as short chain alcohols, water, dimethylformamide, dimethylsulfoxide, acetonitrile and the like.
The negative image undergoes crosslinking and gives desirable patterns which are unchanged in hot solvents.
For example, when a negative image was formed on a film of tetrathiafulvalene bromide the image was subjected to boiling chlorobenzene, dimethylsulfoxide and the like without change. The imase was also subjected to temperatures of 275C in vacuum at 10 6 torr and again without change. These images undergo lift-off readily when treated with aqueous hydrazine for about 1-2 minutes at room temperature.
Negative resist images having dimensions of less than 1 micron, with excellent edge definition of about 0.1 micron, and near vertical walls have been obtained.
No swelling occurred in the images when washed in a wide variety of polar and non-polar solvents.
7 ~l6~7~l Positive resist images can be prepared either in situ or by solvent development. In the in situ rnode the resist is exposed to electron-beam radiatio~ having charge density in the 10 3to 10 1 coul/cm2 range and 5 an energy of from about 5KeV to about 30KeV. At these charge densities levels the exposed resist materials are caused to sublime. This sublimation can be enhanced by heating the substrate upon which the resist lies to temperatures in the range of about 60C to about 100C.
Solvent developed positive images are obtained in those instances where the charge transfer salts do not readily crosslink upon exposure after halogen loss. That halogen loss is effected upon exposure is ascertained by electron microprobe techniques. The exposed materials are readily removed with low polarity solvents such as methylene chloride, chlorform, carbon tetrachloride and the like. The advantage of the solvent development is that in principle more sensitive positive resists can be obtained. An additional feature of solvent development is that less volatile donors used in the image coating process.
Another discovery of the invention disclosed is the different electrical and optical proper~ies ~etween exposed and unexposed materials of the invention.
It was known that the unexposed films were highly conductive having conductivities in the range of from about 0.1 to about 20/ohm-cm. This conductivity i~ of practical advantage because it elminates static charge build up in the film during irradiation.
With prior insulating polymer resists, this problem required that a thin metal layer be deposited on the resi~t. With the present materials this requirement no longer exist. While the unexposed resist exhibits conductivity, the exposed resist is .
1 ~6~7~ 1 found to be insulating. For example, when a film of tetrathiafulvalene bromide is sublimed onto a substrate and its conductivity measured, and compared with the conductivity of the developed electron-beam negative image, it was found that there was change in conductivity of over 8 orders of magnitude. The unexposed resist exhibited a conductivity of 20/ohm-cm, while the exposed regions exhibited a conductivity of less than 10 7/ohm-cm.
It has also been observed that large optical property changes occur in the exposed part of the resist. It is observed that the unexposed resist films strongly absorb light in the visible and near infrared, while the exposed films are non-absorbing in these regions. For example, it is found that films of tetrathiafulvalene bromide have strong absorptions at 5500A and at 3800A. After irra~iation, optical measurements disclosed that these absorptions were absent in the exposed regions. It should be noted that development is not necessary to optically detect electron-beam written patterns on the subject films.
Optical absorption is, of course, dependent upon composition. For example, charge transfer salts such as tetrathiatetracene and tetraphenyl dithiopyran are strongly O O
absorbing in the 8000A to 8500A region. This light absorbing difference in unexposed versus exposed materials lend applications to optical masks and in video storage devices.
The sensitivity of the lithographic process as well as the optical and electrical properties of the present resists are dependent upon respective halogen content and the electron-beam parameters.
Improvement in the sensitivity of the reverse charge ~ 1~S76 1 transfer reaction have been seen in going from tetrathiafulvalene bromide to the chloride salt. This improved the sensitivity by over a factor of 5. In another example, a film of the neutral donor is deposited and then treated with halogen transfer salt with a smaller molar content of halogen. Electron-beam irradiation of this material therefor has to remove less halogen and leads to corresponding enhancement in sensitivity.
The following examples are by way of illustration and not by way of limitation.
Example 1 A film of tetrathiafulvalene bromide of (TTF-Brn) about 5000A thick is prepared by vacuum subliming TTF-Brn at a pressure of 1 micron and a temperature of 185C to about 190C. Sublimation is continued for about 10 minutes.
Analysis of the thus produced film shows a non-stoichrometric composition of TTF-BrO 78.
An image is formed on the film by impinging an electron-beam thereon in a predetermined pattern. The electron-beam had a current density of about 10 4 coulomb/cm2 and an energy of lOKeV. The film is then washed with methanol for about 15 seconds at room temperature to remove the unexposed areas of the film. A negative resist image remained having dimensions less than 1 micron.
The image is unchanged after boiling in chlorobenzene or dimethylsulfoxide and on heating to 275C in vacuum. It is removed however, when it is washed with aqueous hydrazine for about 1-2 minutes at room temperature.
Optical absorption as well as conductivity measurements were made on the film prior and subsequent to exposure. Prior to exposure the film dlsclosed the characteristic TTF-Br salt absorptions at 5500A and 3800A. After exposure these absorptions were absent. Similarly, the conductivity of the film was 20/ohm-cm prior to exposure and was found to be less than 10 7/ohm-cm subsequently.
Example 2 A film of TTF-BrO 78 is prepared as in Example 1. The film is irradiated in a predetermined pattern with a electron-beam having a current density of about 10 3 coulomb/cm and an energy of 10KeV. After irradiation it is found that the exposed film is removed leaving a positive resist image. The image exhibited dimensions of less than one micron with near vertical walls. Further development is not required.
Bxample 3 A film of tetrathiafulvalene chloride (TTF-Clo 65) is prepared as in Example 1 except that a bath temperature of 195C to 205C is used. The stoichiometry of the film is found to be TTF-Clo 65. The film is irradiated and subsequently treated as in Example 1 to effect a negative image. It is found that the solubility, optical and electrical properties are similar to the film deposited in Example 1. It is further found that the TTF-Clo 65 proves to be about 5 times more sensitive that the TTF-BrO 78 film of Example 1.
- ' S 7 ~ t Example 4 A film of TTF-Clo 65 is prepared as in Example 3 and is irradiated and treated as in Example 2. A positlve resist image obtained without solvent developr.lent.
The image has dimensions of less than 1 micron with almost vertical walls.
Example 5 A film of tetrathiafulvalene iodide (TTF-In) is prepared by the procedure disclosed in Example 1 except that a heating temperature of about 140C to about 150C is used. ~nalysis of the film discloses a stoichiometry of TTF-Io 7. The film is irradiated and subsequently treated as the analogous films of Examples 1 and 2 to produce both negative and positive resist images respectively. The solubility, optical and electrical properties are very similar to the films produced in Examples 1 and 2.
Example 6 A film of tetraselenafulvalene bromide (TSeF-Brn) is prepared as in Example 1 to give a film composition of TSeF-BrO 8. This film is irradiated and subsequently treated as in Examples 1 and 2 to give both negative and positive resist images respectively. Optical measurements discloses that the unexposed film have strong absorptions at 43002 and 6500~. Similar changes in solubility, optical and electrical properties as disclosed in Example 1 are observed.
Example 7 Tetrathiatetracene (TTT) is sublimed in vacuum at 1 micron and 350C to give a neutral TTT film. The film is then exposed to bromine vapor for about 10 12 ~1~57fit mins. to provide a conducting film having a stoichiometry of TTT-BrO 1 The film is irradiated and treated in the r,lanner given in Examples 1 and 2 to obtain negative and positive resist images ~hich exhibit similar electrical changes as in the previous Examples.
Halogen salts of the following materials similarly can be used as electron-beam resist and treated in a manner similar to that disclosed in the above examples.
diselenadithiafulvalene dimethyltetrathiafulvalene dimethyltetraselenafulvalene dimethyldiselenadithiafulvalene tetramethyltetrathiafulvalene tetramethyltetraselenafulvalene tetramethyldiselenadithiafulvalene hexamethylenetetrathiafulvalene hexamethylenetetraselenafulvalene hexamethylenediselenadithiafulvalene tetrathianaphthalene tetraselenaphthalene tetrathianaphthalene tetraselenanaphthalene perylene dithiopyran tetramethyldithiopyran tetraphenyldithiopyran diselenapyran tetramethyldiselenapyran tetraphenyldiselenapyran dipyran tetramethylphenylenediamine phthalocyanine nickel phthalocyanine copper phthalocyanine cobalt phthalocyanine 1 1 6 ~ 7~ ~
iron phthalocyanine octamethyltetrabenzporphyrins nic~el octamethyltetrabenzporphyrins The above listing of materials is not meant to indicate that the scope of the invention should be limited thereby. One skilled in the art would know the list not to be exhaustive but that many other compounds derived fro~ those listed above and throughout the specification can also be used in the furtherance of the present invention.
The invention hereinabove described includes a novel class of resist materials which can be generally classified as conducting organic charge transfer salts. These materials can give rise to both negative and positive resists merely by controlling the irradiation parameters, i.e., energy and current density. The resists have other advantages including large changes in solubility, optical and electrical properties which result upon irradiation. These properties lead to their usefulness in the ~abrication of microstructures for large scale integration of electronic circuits, as optical storage media, for fabricating master masks used in photolithography and in eliminating static charging in the resist during electron or ion bombardment.
Claims (72)
1. An electron sensitive resist having a uniform sublimed solid film of a conducting organic charge transfer material selected from the group consisting of neutral halogen salts of each of the following donors;
tetrathiafulvalene and its alkyl derivatives, tetraselenafulvalene and its alkyl derivatives, tetraheterotetracenes having the general structural formula:
where X is S and/or Se; tetraherteronaphthalenes having the general structural formula:
where X is S and/or Se; perylene, tetramethylphenylenediamines, phthalocyanines and porphyrins and wherein said halogen is selected from chlorine, bromine and iodine.
tetrathiafulvalene and its alkyl derivatives, tetraselenafulvalene and its alkyl derivatives, tetraheterotetracenes having the general structural formula:
where X is S and/or Se; tetraherteronaphthalenes having the general structural formula:
where X is S and/or Se; perylene, tetramethylphenylenediamines, phthalocyanines and porphyrins and wherein said halogen is selected from chlorine, bromine and iodine.
2. An electron sensitive resist according to claim 1 wherein said conducting organic charge transfer material is a halogen salt of tetrathiafulvalene.
3. An electron sensitive resist according to claim 1 wherein said conducting organic charge transfer material is a halogen salt of tetraselenafulvalene.
4. An electron sensitive resist according to Claim 1 wherein said conducting organic charge transfer material is a halogen salt of tetrathiatetracene.
5. An electron sensitive resist according to Claim 1 wherein said conducting organic charge transfer material is a halogen salt of diselenadithiafulvalene.
6. An electron sensitive resist according to Claim 1 wherein said conducting organic charge transfer material is a halogen salt of dimethyltetrathiafulvalene.
7. An electron sensitive resist according to Claim 1 wherein said conducting organic charge transfer material is a halogen salt of dimethyltetraselenafulvalene.
8. An electron sensitive resist according to Claim 1 wherein said conducting organic charge transfer material is a halogen salt of dimethyldiselenadithiafulvalene.
9. An electron sensitive resist according to Claim 1 wherein said conducting organic charge transfer material is a halogen salt of tetramethyltetrathiafulvalene .
10. An electron sensitive resist accordlng to Claim 1 wherein said conducting organic charge transfer material is a halogen salt of tetramethyltetraselenafulvalene.
11. An electron sensitive resist according to Claim 1 wherein said conducting organic charge transfer material is a halogen salt of tetramethyldiselenadithiafulvalene.
12. An electron sensitive resist according to Claim 1 wherein said conducting organic charge transfer material is a halogen salt of hexamethylenetetrathiafulvalene.
13. An electron sensitive resist according to Claim 1 wherein said conducting organic charge transfer material is a halogen salt of hexamethylenetetraselenafulvalene.
14. An electron sensitive resist according to Claim 1 wherein said conducting organic charge transfer material is a halogen salt of hexamethylenediselenadithiafulvalene.
15. An electron sensitive resist according to Claim 1 wherein said conducting organic charge transfer material is a halogen salt of tetrathianaphthalene.
16. An electron sensitive resist according to Claim 1 wherein said conducting organic charge transfer material is a halogen salt of tetraselenanaphthalene.
17. An electron sensitive resist according to Claim 1 wherein said conducting organic charge transfer material is a halogen salt of tetrathiatetracene .
18. An electron sensitive resist according to Claim 1 wherein said conducting organic charge transfer material is a halogen salt of tetraselenatetracene.
19. An electron sensitive resist according to Claim 1 wherein said conducting organic charge transfer material is a halogen salt of perylene.
20. An electron sensitive resist according to Claim 1 wherein said conducting organic charge transfer material is a halogen salt of dithiopyran.
21. An electron sensitive resist according to Claim l wherein said conducting organic charge transfer material is a halogen salt of tetramethyldithiopyran.
22. An electron sensitive resist according to Claim 1 wherein said conducting organic charge transfer material is a halogen salt of tetraphenyldithiopyran.
23. An electron sensitive resist according to Claim 1 wherein said conducting organic charge transfer material is a halogen salt of diselenapyran.
24. An electron sensitive resist according to Claim 1 wherein said conducting organic charge transfer material is a halogen salt of tetramethyldiselenapyran.
25. An electron sensitive resist according to Claim 1 wherein said conducting organic charge transfer material is a halogen salt of tetraphenyldiselenapyran.
26. An electron sensitive resist according to Claim 1 wherein said conducting organic charge transfer material is a halogen salt of dipyran.
27. An electron sensitive resist according to Claim 1 wherein said conducting organic charge transfer material is a halogen salt of tetramethylphenylenediamine.
28. An electron sensitive resist according to Claim 1 wherein said conducting organic charge transfer material is a halogen salt of phthalocyanine.
29. An electron sensitive resist according to Claim 1 wherein said conducting organic charge transfer material is a halogen salt of nickel phthalocyanine.
30. An electron sensitive resist according to Claim 1 wherein said conducting organic charge transfer material is a halogen salt of copper phthalocyanine.
31. An electron sensitive resist according to Claim 1 wherein said conducting organic charge transfer material is a halogen salt of cobalt phathalocyanine.
32. An electron sensitive resist according to Claim 1 wherein said conducting organic charge transfer material is a halogen salt of iron phthalocyanine.
33. An electron sensitive resist according to Claim 1 wherein said conducting organic charge transfer material is a halogen salt of octamethyltetrabenzporphyrins.
34. An electron sensitive resist according to Claim 1 wherein said conducting organic charge transfer material is a halogen salt of nickel octamethyltetrabenzporphyrins.
35. A method for forming resist images including the steps of:
(a) applying onto a substrate a uniform solid film of a conducting organic charge transfer material selected from the group consisting of halogen salts of; tetrathiafulvalene and its alkyl derivatives, tetraselenafulvalene and its alkyl derivatives, tetrathiatetracenes, tetraselenatetracenes, di-thiadiselenatetracenes, tetramethylphenylenediamine, tetraselenanaphthalene, tetrathianaphthalene, dithiadiselenanaphthalene, dithiopyran, tetramethyldithiopyran, tetraphenyldithiopyran, diselenapyran, tetramethyldiselenapyran, tetraphenyldiselenapyran, dipyran, phthalocyanines and porphyrins and wherein said halogen is selected from chlorine bromine and iodine, and (b) exposing said film to an electron-beam in a predetermined pattern, said electron-beam having sufficient energy and current density to either cause exposed areas of said film to voltalize where a positive resist image is required, or cause cross-linking in exposed areas of said film when a negative resist image is required.
(a) applying onto a substrate a uniform solid film of a conducting organic charge transfer material selected from the group consisting of halogen salts of; tetrathiafulvalene and its alkyl derivatives, tetraselenafulvalene and its alkyl derivatives, tetrathiatetracenes, tetraselenatetracenes, di-thiadiselenatetracenes, tetramethylphenylenediamine, tetraselenanaphthalene, tetrathianaphthalene, dithiadiselenanaphthalene, dithiopyran, tetramethyldithiopyran, tetraphenyldithiopyran, diselenapyran, tetramethyldiselenapyran, tetraphenyldiselenapyran, dipyran, phthalocyanines and porphyrins and wherein said halogen is selected from chlorine bromine and iodine, and (b) exposing said film to an electron-beam in a predetermined pattern, said electron-beam having sufficient energy and current density to either cause exposed areas of said film to voltalize where a positive resist image is required, or cause cross-linking in exposed areas of said film when a negative resist image is required.
36. A method for forming a positive resist image according to Claim 35 wherein said electron-beam has an energy of from about 5-30KeV and a charge density in the 10-3 couiomb/cm2 range.
37. A method for forming a negative resist image as defined in Claim 35 including the further step of:
treating the unexposed areas of said film with a suitable solvent to remove said unexposed areas.
treating the unexposed areas of said film with a suitable solvent to remove said unexposed areas.
38. A method according to Claim 37 wherein said electron-beam has an energy of about 5 KeV to about 30 KeV and a charge density of at least 10-4 coulombs/cm2.
39. A method according to Claim 36, 37 or 38 wherein said conducting organic charge transfer material is a halogen salt of tetrathiafulvalene.
40. A method according to Claim 36, 37 or 38 wherein said conducting organic charge transfer material is a halogen salt of tetraselenafulvalene.
41. A method according to Claim 36, 37 or 38 wherein said conducting organic charge transfer material is a halogen salt tetrathiatetracene .
42. A method according to Claim 36, 37 or 38 wherein said conducting organic charge transfer material is a halogen salt of diselenadithiafulvalene.
43. A method according to Claim 36, 37 or 38 wherein said conducting organic charge transfer material is a halogen salt of dimethyltetrathiafulvalene.
44. A method according to Claim 36, 37 or 38 wherein said conducting organic charge transfer material is a halogen salt of dimethyltetraselenafulvalene.
45. A method according to Claim 36, 37 or 38 wherein said conducting organic charge transfer material is a halogen salt of dimethyldiselenadithiafulvalene.
46. A method according to Claim 36, 37 or 38 wherein said conducting organic charge transfer material is a halogen salt of tetramethyltetrathiafulvalene.
47. A method according to Claim 36, 37 or 38 wherein said conducting organic charge transfer material is a halogen salt of tetramethyltetraselenafulvalene.
48. A method according to Claim 36, 37 or 38 wherein said conducting organic charge transfer material is a halogen salt of tetramethyldiselenadithiafulvalene.
49. A method according to Claim 36, 37 or 38 wherein said conducting organic charge transfer material is a halogen salt of hexamethylenetetrathiafulvalene.
50. A method according to Claim 36, 37 or 38 wherein said conducting organic charge transfer material is a halogen salt of hexamethylenetetraselenafulvalene.
51. A method according to Claim 36, 37 or 38 wherein said conducting organic charge transfer material is a halogen salt of hexamethylenediselenadithiafulvalene.
52. A method according to Claim 36, 37 or 38 wherein said conducting organic charge transfer material is a halogen salt of tetrathianaphthalene.
53. A method according to Claim 36, 37 or 38 wherein said conducting organic charge transfer material is a halogen salt of tetraselenanaphthalene.
54. A method according to Claim 36, 37 or 38 wherein said conducting organic charge transfer material is a halogen salt of diselenadithianaphthalene.
55. A method according to Claim 36, 37 or 38 wherein said conducting organic charge transfer material is a halogen salt of tetraselenatetracene.
56. A method according to Claim 36, 37 or 38 wherein said conducting organic charge transfer material is a halogen salt of perylene.
57. A method according to Claim 36, 37 or 38 wherein said conducting organic charge transfer material is a halogen salt of dithiopyran.
58. A method according to Claim 36, 37 or 38 wherein said conducting organic charge transfer material is a halogen salt of tetramethyldithiopyran.
59. A method according to Claim 36, 37 or 38 wherein said conducting organic charge transfer material is a halogen salt of tetraphenyldithiopyran.
60. A method according to Claim 36, 37 or 38 wherein said conducting organic charge transfer material is a halogen salt of diselenapyran.
61. A method according to Claim 36, 37 or 38 wherein said conducting organic charge transfer material is a halogen salt of tetramethyldiselenapyran.
62. A method according to Claim 36, 37 or 38 wherein said conducting organic charge transfer material is a halogen salt of tetraphenyldiselenapyran.
63. A method according to Claim 36, 37 or 38 wherein said conducting organic charge transfer material is a halogen salt of dipyran.
64. A method according to claim 36, 37 or 38 wherein said conducting organic charge transfer material is a halogen salt of tetramethylphenylenediamine.
65. A method according to Claim 36, 37 or 38 wherein said conducting organic charge transfer material is a halogen salt of phthalocyanine.
66. A method according to Claim 36, 37 or 38 wherein said conducting organic charge transfer material is a halogen salt of nickel phthalocyanine .
67. A method according to Claim 36, 37 or 38 wherein said conducting organic charge transfer material is a halogen salt of copper phthalocyanine .
68. A method according to Claim 36, 37 or 38 wherein said conducting organic charge transfer material is a halogen salt of cobalt phthalocyanine .
69. A method according to Claim 36, 37 or 38 wherein said conducting organic charge transfer material is a halogen salt of iron phthalocyanine.
70. A method according to Claim 36, 37 or 38 wherein said conducting organic charge transfer material is a halogen salt of octamethyltetrabenzphorphyrins.
71. A method according to Claim 36, 37 or 38 wherein said conducting organic charge transfer material is a halogen salt of nickel octamethyltetrabenzporphyrins.
72. A method according to claim 36, 37 or 38 wherein said conducting organic charge transfer material is a halogen salt of diselenadithiatetracene.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US6529179A | 1979-08-09 | 1979-08-09 | |
| US065,291 | 1979-08-09 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1165761A true CA1165761A (en) | 1984-04-17 |
Family
ID=22061674
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000354062A Expired CA1165761A (en) | 1979-08-09 | 1980-06-16 | Class of e-beam resists based on conducting organic charge transfer salts |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP0023988B1 (en) |
| JP (1) | JPS5627139A (en) |
| CA (1) | CA1165761A (en) |
| DE (1) | DE3066749D1 (en) |
| IT (1) | IT1149813B (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4522754A (en) * | 1982-11-12 | 1985-06-11 | Ciba Geigy Corporation | Metallically conducting (2-fluoro-5,6,11,12-tetraselenotetracene)2 -bromide |
| US4601853A (en) * | 1984-02-13 | 1986-07-22 | Ciba-Geigy Corporation | (2-fluoro-5,6,11,12-tetraselenotetracene)2 chloride |
| CH664963A5 (en) * | 1985-10-18 | 1988-04-15 | Ciba Geigy Ag | DIFLUORED (5,6,11,12-TETRASELENOTETRACEN) 2-HALOGENIDES, METHOD FOR THE PRODUCTION AND USE THEREOF. |
| JPS6435545A (en) * | 1987-07-31 | 1989-02-06 | Japan Synthetic Rubber Co Ltd | Resist composition used for processing with charged particle beam |
| JPH01210944A (en) * | 1988-02-18 | 1989-08-24 | Japan Synthetic Rubber Co Ltd | Radiation sensitive resin composition |
| EP0362143B1 (en) * | 1988-09-30 | 1995-11-15 | Ciba-Geigy Ag | Antistatic and electrically conductive relief images, process for manufacturing the same, coating material and radiation-sensitive polymers |
| JP5458267B2 (en) * | 2009-02-24 | 2014-04-02 | 国立大学法人東京工業大学 | Hexamethylenetetrathiafulvalene compound, organic semiconductor and organic thin film transistor |
| CN113004291B (en) * | 2019-12-20 | 2022-03-01 | 中国科学院化学研究所 | Metalloporphyrin-based molecular glass chemical amplification photoresist and preparation method and application thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3925076A (en) * | 1971-02-16 | 1975-12-09 | Monsanto Co | Light sensitive compositions and products |
| US4312991A (en) * | 1979-05-10 | 1982-01-26 | International Business Machines Corporation | Dithiobenzoate 4,5-dicyano-1,3-(dithiolidene-2-yl)methylene |
-
1980
- 1980-06-09 JP JP7677080A patent/JPS5627139A/en active Granted
- 1980-06-16 CA CA000354062A patent/CA1165761A/en not_active Expired
- 1980-07-18 EP EP80104214A patent/EP0023988B1/en not_active Expired
- 1980-07-18 IT IT23528/80A patent/IT1149813B/en active
- 1980-07-18 DE DE8080104214T patent/DE3066749D1/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| EP0023988B1 (en) | 1984-02-29 |
| EP0023988A2 (en) | 1981-02-18 |
| DE3066749D1 (en) | 1984-04-05 |
| IT1149813B (en) | 1986-12-10 |
| EP0023988A3 (en) | 1982-01-20 |
| JPS6245969B2 (en) | 1987-09-30 |
| JPS5627139A (en) | 1981-03-16 |
| IT8023528A0 (en) | 1980-07-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4312935A (en) | Class of E-beam resists based on conducting organic charge transfer salts | |
| Lai | Polymers for electronic applications | |
| CA1071455A (en) | High sensitivity resist system with separably developable layers | |
| JP2657956B2 (en) | Electrically conductive polymer material | |
| US5589270A (en) | Processed substrate obtained by a process for effecting suppression of electrification | |
| US5137799A (en) | Electrically conductive resist material, a process for its preparation and its use | |
| CA1165761A (en) | Class of e-beam resists based on conducting organic charge transfer salts | |
| US4312936A (en) | Class of E-beam resists based on conducting organic charge transfer salts | |
| US4548893A (en) | High resolution lithographic resist and method | |
| US4096290A (en) | Resist mask formation process with haloalkyl methacrylate copolymers | |
| US4338392A (en) | Class of E-beam resists based on conducting organic charge transfer salts | |
| KR930010221B1 (en) | Method of forming pattern by using an electroconductive compound | |
| US4348472A (en) | Method of applying a layer in accordance with a pattern on a substrate, a negative resist material and a substrate coated with the resist | |
| US4363829A (en) | Process for forming an electrically conductive film | |
| JPS5857096B2 (en) | Zoukeiseihouhou | |
| US3916036A (en) | Sensitized decomposition of polysulfone resists | |
| US4264715A (en) | Method of preparing resist pattern | |
| JPS58116532A (en) | Pattern formation | |
| US4262083A (en) | Positive resist for electron beam and x-ray lithography and method of using same | |
| US4027052A (en) | Fabrication of iron oxide pattern | |
| US4456678A (en) | High resolution lithographic resist of negative working cationic vinyl polymer | |
| US4474869A (en) | Polyvinylpyridine radiation resists | |
| Tomkiewicz et al. | Organic conductors as electron beam resist materials | |
| CA1220375A (en) | High resolution lithographic resist and method | |
| US4581318A (en) | N-alkynyl polyvinylpyridinium resists having electron and deep U.V. sensitivity |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |