CA1161685A - Class of x-ray resists based on donor polymer-doped halocarbon acceptor transfer complexes - Google Patents

Class of x-ray resists based on donor polymer-doped halocarbon acceptor transfer complexes

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Publication number
CA1161685A
CA1161685A CA000358898A CA358898A CA1161685A CA 1161685 A CA1161685 A CA 1161685A CA 000358898 A CA000358898 A CA 000358898A CA 358898 A CA358898 A CA 358898A CA 1161685 A CA1161685 A CA 1161685A
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polymer backbone
donor molecule
molecule bonded
donor
polymer
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French (fr)
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Ari Aviram
Donald C. Hofer
Frank B. Kaufman
Steven R. Kramer
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International Business Machines Corp
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International Business Machines Corp
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Abstract

ABSTRACT

new class of X-ray resists are described. The resists are donor polymer-doped halocarbon acceptor transfer complexes. They are prepared from known polymeric backbones such as polyvinylchloride, polyglutamic acid, polyvinylbenzylchloride, polyepichlorohydrin, poly(.alpha.halophosphazenes), polyacrylic chloride, polystyrene and the like, and donor molecules such as tetrathiafulvalenes, tetraselenafulvalenes, dithiadiselenafulvalene, ferrocenes, phenothiazines, pyrazoline and an amine having the general formula R-NH2 where R
can be selected from alkyl and aryl groups. A
lithographic method is also described.

Description

e~

NEW CLi'~SS OF X-RAY RE:SISTS BI~SED ~N DONOR
POLYMER--DOPEI:) HALOCARBON ~CCEPTOR
TRANSFER COMPLEXES

Bl~CKGROUND OF T~IE INVE:NTION

Field of the Inve~ntion The invention Lies in the field of X-ray resist compositions and the production of patterned thin film layers thereErom.

. Prior Art The prior a.rt is replete with radiation sensitive materials as resists and with their use in pattern formation in the fabrication of micro-electronic (1evices. In tllc prior ~rt, pattcrn formation in these materials is dependent upon differential solubility between irradiated and unirradiated regions. These solubility changes are produce~ 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.

1 Several prior art resists have included in them halogen containing organic compounds or halocarbons. These halocarbons are generally present to enhance the sensi-tivity of the resist. Several such resists are dis-cussed and reviewed in U.S. Patents 3,752~669; 3,7~9,023;
3,820,993; 3,895,954; 3,988,152 and 3,316,036. The resists disclosed in the above references are sensitive to either actinic or electron beam radiation. ~he prime need for the halocarbon in these resists are for the generation of free radicals to initiate polymerization.

More recently there has been developed a new class of E-beam resist materials based Oll donor-charge transfer salts. These resist materials are described in Canadian patent application 354,062, filed June 16, 1980, by E.M.
Engler et al and assigned to the assignee of the present application and is entitled "Class Of E-Beam Resists Based Qn Conducting Organic Charge Transfer Salts".
These materials are different and distinct from the pre-sent compositions in that they are crystalline saltsthat are coated onto a substrate by evaporation or sub-limination, wherein the present compositions are amor-phous polymeric materials which are cast from a solu-tion. The present resist compositions are two compo-nent systems in which differential solubility is gener-ated via salt formation as opposed to the one compo-nent system of the above-mentioned application in which a neutral substance is produced. Additionally, the materials used in the present invention are in-sulating while the aforementioned are conductive.

The prior art materials have several drawbacks amongwhich is the difficulty of obtaining sharp images of high resolution, particularly in negative resists.
This is due to the swelling of the polymeric material during solvent development.

SUMMARY OF THE INVENTIO~
What has been discovered here are novel X-ray negative resists which can be broadly classified as donor polymer-doped halocarbon charge transfer complexes. More specifically, the materials comprise a polymer bac]cbone or skeleton having bonded thereto electroactive molecules.
These electroactive polymer species are doped with a halocarbon.

BRIEF DESCRIPTION OF THE DRA~7INGS
FIG. 1 shows graphically the relationship between the exposure dose and the normalized thickness of the exposed resist.

~IG. 2 and FIG. 3 show X-ray exposed patterns via scanning electron microscopy.

DESCRIPTION OF THE INVENTION
The present invention teaches novel X-ray resist materials which can be used to provide a negative resist image.
Principally, the materials are comprised of electroactive polymers and a halocarbon. The resist includes a donor polymer-doped halocarbon charge transfer complex.
Preferably, the electroactive polymer consists of a polymer backbone and an electroactive molecule bonded thereto.
Several of -the electroactive polymers of the type anticipated for use in this invention are described in U.S~
Patent No. 4,142,783 and in the IBM* Technical Disclosure Bulletin, Vol. 20, #7, December 1977.

The polymeric backbone can be selected from several known homopolymer and copolymer compositions having skeletal functional groups or side chains having functional groups capable of reacting with the functional groups of donor molecules. Polymers which can be used, include polystyrene, a copolymer o~ polystyrene and chloromethylated styrene, e.g., *Registered Trade Mark Of International Business Machines Corporation CH2C~

~(CH2-CH)x (CH2-CH)I-~ ]n where the value of X is varied (O<x<l), so that the number of donor molecules per chain and their distance apart can be varied. The desired lithographic properties are thus varied as a function of X;

Typically, other polymer backbones can be selected from the following:
polyglutamic acid ~C--CH-N~n ~CH2)2 COOH

polyvinyl chloL-ide ~; [-CH2-CH
CQ

polyepichlorohydrin [(-C~2-CH-O~]
~2 C~

poly(~halophosphazenes~

r X Rl _ - N - P t R Xln poly(acrylic chLoride) ~CH -CH ~n ' COOC~

and the like.

The donor molecules that can be used in this invention are those which can be char~cterizcd as having the following specific molecular properties:

(a) Those that are capable of electron oxidation to a cation.

~b) Have an oxidation potential of from about O.lV
to about lV measured against a standard calomel electrode;

(c) those that photoionize in the presence of a halocarbon; and lS (d) which have a functional group whlch when reacted with a polymer support will be bond~d thereto.
Functlonal groups contemplated by the present invention include hydroxyl, phenoxy, carboxyl, amino ~- groups and the like.

20- A wide variety of ~ donor molecules are expected to be active in polymeric form as negative resist materials.

This invention may be effected by using donors of the empirical formula C6H4X4R~ and having the structural formula F?l~¢X~ (X~ R 3 where X=O, S, Se and Te or any combination thereof.
T~e R groups may be of any organic substituent including alkyls, such as methyl and ethyl, phenyls, substituted phenyls, -SCH3, -CO2ME, halogen, fused cyclics in which the substituent effectively connec-ts Rl with R2 and R3 with R4, e.g. Some specific fulvalene compositions include tetrathiaulva1ene (TTF), its derlvatives and Se analogs (TSeF) and its derivatives. For example, tetrathiafulv~lenecarboxylic acid (l'l~O?II), tetraselenafulvalenecarboxylic, ~hydroxyrnethyl)-tetrathiafulvalene (TTFC1l2O~I), hydroxymethyl-tetraselenafulvalene (TSeFC~l2O~I), (p-hydroxyphenyl)-tetrathiafulvalene (TTFC6~l4O~I), (p hydroxyphenyl)-tetrasclcnilEI~l.val.etlc (TSeF(:GII~OII), (p~ llin~ llcny1)-tetra~llia~ulvalcne (TTFC6ll4Nll2), (p-carboxyphc!nyl)-tetrathiafulvalene (TTFC6ll4CO2ll), phenoxy (TTF).
Qf~x~

The followi.ny fuscd rings, such ~.s cyclo~)cntene, cyclohexene, benzene, furan, thiophene, clihydrofuran and dihydrothiophene, and derivatives ttlereof can be used. In addition, tctr~thiatctraccrle com~ounds, e.g.
S~ S
C~
S--S

YO979-0~0 and their derivatives are also suitable for the purpose of this invention. In general, organic ~-electron donors havinq low ionization potentials (<7.5eV)2 can be used.

Additionally, the following compositions are contemplated by this invention;

A~ines R-NH2j R=Alkyl, Aryl Pyrazolines 1 0 qS 5 ~N
I
\~3 ~ Pyrazolines of particular importance include ; 1,3-di-(p-met}loxy~henyl)-5-(y-hydroxypllellyl)-~2-pyrazoline, 1, 5-di-(p-methoxyphenyl)-3-(p-hydroxyphenyl)-A2-pyrazoline, 3, 5-di-(p-methoxyphenyl)-1-(p-hydroxyphenyl)-~2_ pyrazoline, 1, 3-di-lp-methoxyphenyl)-5-(p-carboxypllcnyl)-A2-pyrazoline;
1, 5-di-(p-methoxyphenyl)-3-(p-carboxyphenyl)_Q2_ pyrazoline, 3, 5-di-~p-methoxyphenyl)-1-(p-carboxyphenyl)-~2-pyrazoline, 1, 3~di-(p-methoxypheny13-5-(p-aminophenyl)-Q2-: 25 pyrazoline, 1, 5-di(phctlyl)-3-(p-aminophellyl)-A2-~)yra%olinc, l-(p hydroxyphenyl)-3-(p-methoxystyryl)-5-(p-methoxyphenyl)-~2-pyrazoline, l-(p-hydroxyphenyl)-3-(p-diethylaminostyryl) 5-(p-diethylaminophenyl)-~2-pyrazoline, YO979-0~0 1 Ferrocene <~
m ~ ~ m = Fe, etc.
~' Phenothiazine ~ 10 ~1 -lS [(~ -C5H5)Fe(CO)]4 Dithiadiselenafulvalene and its derivatives may also be used as donor molecules.

The acceptor molecules that can be used in this invention are those which can be characterized as having the following specific molecular properties:

a) Contains one or more halogen atoms.
(b) Has high electron affinity to accept electron from donor species (0-2eV)O

(c) Forms anionic species.
~30 Typical halocarbon acceptors which can be used are selected from CC14, CBr4, CI4, C2 C16' C2 C12 4' 3 4 4
2 2 4' 2 2C14~ C2Br6~ ~3C18~ Cl C C13l CHBr , CHCl CH2C12 and the like.
The halocarbon agent may be present in amounts ranging from 0.01 to 10 times the concentration of the donor moiety.

~' There are two basic kinds of synthetic procedures for covalently attaching the donor molecules to the polymer resin. In equation (1~, ~ ~ ~ CH2x~ D- y ~ ~3 ~

where ~is a polymer, x is a halogen, D is a donor molecule, and y is a functional group capable of coupling D to the benzene ring. In this procedure, preformed and appropriately functionalized donor molecules tD-Y~ are reacted in single-step coupling procedures with the polymer resin. In this approach, the groups -x and -y are chosen so as to lead to coupled products. Bonding to the polymer matrix is accomplished in one step. In an altern~te method, ti.e. reactions 2-4), the desired electroactlve molecule is synthesi.zetl ~rom polymer precursors directly on the resin.
; Thus, functionalized electroactive species are not required; however, multiple polymer reactions become necessary.

' O
C ¢S ~, ~ C l l z o--C ¢ 5~

~ ¢ ~ ~ C H2 -C--TT F

1 The specific steps of the synthesis of the contemplated compositions can be found in aforementioned U.S. Patent No. 4,142,783.

The solvents whieh ean be used for film eoating are toluene, chloroform, methylene chloride, eyclopentanone, tetrahydrofuran, methyl ethyl ketone etc.

In the present invention resist compositions are exposed to x-ray radiation.

Exposures were performed in a 10 6 torr. vaeuum, using a vacuum generator 1 ReV electron gun (model ~VGl), with 7 KV gun voltage and 40 ma gun current. The x-rays having an energy of about 1.34 KeV are generated with an Al tar-get (8.3A) and x-ray spot of 1-2mm size. A gold (6000A) mask on a polyimide substrate is coated with 500A of Al to prevent optical exposure of the resist. The mask-wafer separation used is 4~m, and the copy is obtained at a gun-wafer separation of 18cm. Under these conditions the copy time for a 100 mj/cm2 dose is about three hours.
X-ray exposures involve doses of 25-100 mj/cm .

More specifically, this invention concerns new compositions of matter which function in a novel resist process when irradiated by X-rays. For example, films of a polymerie TTF materials can be spin east from a solution eontain-ing a haloearbon aeeeptor, sueh as CBr4~ Under these eonditions the resulting polymer film eontains CBr4 and becomes sensitive to radiation. When X-rays are used to irradiate these films through appropriate masks, only the unexposed li areas can be removed from the underlylng substrate by washinc3 with a non-polar solveht. This negative resist process is a novel one and unrelated ; to those suggested earlier for polymers whose solubility decreases upon exposure to radlation because of radiation induced crosslinkin~ reactions.

It is suggested that these resists operate by means .the radiation-induced formation of a salt according to Reaction 1 where the Poly (TTF) + CBr4 ~ poly (TTF.~ ~Br ) (1) The neutral polymer is soluble in non-polar solvents while the salt produced is insoluble. This reaction is known to occur in monomeric TT~
in solution U. S. Patent No. 4 036 648 where the halide salt produced is insolu~le in non-polar solvents. This new mechanlsm for lithographic action has been established in the following ways.

Using visible-rlca~ ir spcctropllotometry thc TTF
ions postulated in the above reactiorl have been detected. By irradiating poly~TTF) doped halocarbon films that were spun onto transparent substrates. It has been observed that the films spectrum changes during irradiation to give new absorptions at 600nm and at 800nm previously identified as characteristic of TTF ion and aggregates thereof. (See the publication to J. B. Torrancc ct al entitlcd oEtic l rropcrties of the Radical Cation Tetrathiafulvalenium in its Mixed-Valence and ~lonovalence ~alide Salts Phys. Rev. B 19 730 (1979)). ~dditional predictions of the suggested mechanism have also .

1 been observed. For instance, it would be expected tha-t polymer films containing no halocarbon present would be much less sensitive to incident radiation.
Confirming this point, it has been ohserved that irradiation of the undoped TTF polymer films have no lithographic images when subjected to the same incident radiation as in the case of doped films.
.
Another facet of this mechanism is that reversing of the charge transfer in Reaction 1, see Reaction 2 below, could be expected to lead to a change in the solubility properties, whereby, the irradiation poly(TTF ) (X ) -~ poly TTF (2) process would be nullified and removal of the polymer (now in its neutral state) could take place. This effect has been demonstrated in the following way.
An exposed film was found to be insoluble in the organic solvent dimethylformamide (D~F). ~owever, when the chemical reducing agent hydrazine is added to the DMF solution, it was ohserved that the exposed polymer fi]m was readily removed leaving a clean Si substrate. In this process, hydrazine reduces the oxidized TTF back to its neutral form TTF and the neutral polymer, thus formed can he readily dissolved in the organic solvent.

The third ramification of the postulated mechanism is that other ~-donor polymers should be lithographically active in the presence of halocarbon dopants. As alluded to previously, ~-donor sensitivity to radiation with halocarbons present has been ohserved for a large number of donors in fluid solution. If the postulated Y09~79 040 1 mechanism is correct it would be expected that the same variety of donor halocarbon ionization found in solution would also be observed in the polymeric solid state. Similar lithographic differential solubility with donors such as pyrazoline, ; dimethylphenylenediamine, and ferrocene bound to polymeric backbones and prepared as halocarbon doped films, has in fact been observed.

A prime disadvantage of previous negative resist materials are the inherently low resolution of the patterns obtainable. As discussed earlier, negative resists typically operate by means of a - radiation-induced cross~linking process. Although the cross-lin]ced polymer that remains cannot be dissolved in a developer solvent, penetration of the solvent into the polymer causes swelling of the polymer chains since many of the development solvents are thermodynamically good solvents for the unexposed non-crosslinked polymer. The swelling process grossly distorts the lithographic pattern and attempts to alleviate this problem by use of mixed solvents or thermal treatments have largely been unsuccessful.
For the present resist process, however, the lithographic patterns obtained showed no evidence :
for solvent induced distortions or loss of resolution. It is suggested that solvent penetration of the polymer followed by swelling is prevented in the system described herein, by the presence of ions which act to repel the non-polar solvent ~rom the polymer matrix. Thus solvent cannot penetrate into the exposed polymer mass and cause swelling.

~09-79-0~0 The following examples are given solely for purposes of illustration and are not to be construed as limitations on the inventions, many variations of which are possible without departing from the spirit c~r scope thereof.

Poly (vinylcarboxytetrathiafulvalene) Poly(vinylbenzylchloride), prepared from the monomer vin~l-benzylchloride, 0.275g, and the cesium salt of tetrathia-fulvalene carboxylic acid, 0.750mg, is added to 75 ml of a DMF solvent and stirred at 75C for 24 hours. The solu-tion is concentrated and the resultant polymer is isol~ted by precipitation into a rapidly stirred H2O solution. Re-peated precipitations from T~IF/H2O gave a dark brown solid.
Anal. calc'd for C15 1 Hll.6S3.5 1.7 C 0.13 9 9 ( 7 4 3O2)0.87(Cl~0.l3] C=53.81, S=33.0g~ cl=o.l4.
Found C,53.74; S,32.96; Cl,0.23.

Polymer films are prepared by mixing 4.7mg of the polymer with l mg of C2Br2C14 which is added to 20~1 of cyclopen-tanone. The films are spin coated at 2500 RPM on a photo-; resist spinner. No baking is required in order to obtain good images. Solvents used as developers include tetra-hydrofuran, cyclopentanone, diglyme, methylene chloride, chloroform and mixtures thereof.
Several poly (TTF) films are prepared in this manner. To determine the sensiti~ity of this resist, these films were exposed to X-rays at energies ranging YO9-79-0~0 1 from 15-100 mj/cm2. The films were developed in (THF), and then the thickness of the remaining resist was deter-mined. From the resulting plot of normalized thickness remaining vs. dose rate, see FIG. 1, it can be seen that the sensitivity of the material for 50~ thickness remain-ing is ~ 44mj/cm2. From data on other resist materials (Table I), it can be seen that the present material is one of the most sensitive resists known.

Determination of Resolution of Resist:

An X-ray exposed pattern was studied via scanning electron microscopy (see FIG. 2). These photographs shown no evi dence for the classical negative resist swelling behaviour.
All of the patterns are extremely well formed, with parallel vertical walls and showiny no signs of pattern distortion.
From the indicated scale, it is estimated that the present resist has a resolution of better than 2000A.

EX~MPLE 2 Poly (vinylcarboxyferrocene) Poly (vinylben~ylchloride), (150mg) is reacted with the 360 mg of ceslum salt of ferrocene carboxylic acid, (as prepared below) in 65ml DMF solvent. The solution is heated to 75C, and stirred for 24 hours. The volume of the solution is reduced and the polymer is precipi-tated into H2O. Repeated precipitations (THF/H2O) gave a light yellow solid. Anal. calc'd for CgHg(C7 5H5 ~l 4 FeO 7) (Clo 3) C,69.9; Fe,13.4; Cl,4. Found C,67.62;
Fe 12.11; Cl,4.61.

s 1 Cesium salt of carboxyferrocene. Monocarboxyferrocene 230 mg, is dissolved in ethanol. To this solution is added 5ml of H2O which contained 250 mg CsHCO3. Using slight heating, and high vacuum, the solution was taken to dryness to produce the desired salt.

About 5.2 mg of -the so prepared polymer and about lmg of C2Br2C14, the acceptor compound are added to 261ll of THF solvent and films are spun at 2500 RPM on a photo-resist spinner. The films are exposed to X-rays having energies in the range 10-lOOmj/cm2. Patterns are developed by one of the following solvents or mixtures thereof:
toluene, chloroform, methylene chloride, cyclopentanone, THE.

No pre- or post-exposure baking is required to obtain good images.

Poly (vlnylphenoxy-1,3-(p methoxyphenyl)-5-,~
(p-hydr~oxyphenyl)-~-pyraæoline):

The potassium salt of the pyrazoline is prepared by add-ing 374mg pyrazoline to 40 mg KH in dry THF. After stirring for 30 minutes, 152mg of polyvinylbenzylchloride is added to this solution. After refluxing for 4 days, the solvent volume was reduced and the polymer isolated following multiple reprecipitations from 50:50 MeOH/H2O. About 4.6mg of the polymer (4.6mg) and lmg of the C2Br2C14 acceptor, are added to 32~1 of THF. Films were spun at 2500 RPM on a photoresist spinner. After x-ray exposures as in the above examples, good images were obtained by developing 1 in toluene: THF mixtures. No pre- or post-exposure baking was required to obtain good images Poly[p-N,N-dimethylamino)-N-~-D-glutamanilide) Poly(D-glutamic acid) (Miles-Yeda Ltd. mol wt 12400), 0.5g is dissolved in 50 mL of dry DMF and 2g of freshly distilled N, N-dimethyl-p-phenylenediamine is then addedO
The solution is cooled to 0C and lg of DCC is added with stirring. Stirring is continued at 0C for lh and at room temperature for an additional 24 h. One milliter of dry methanol is added and stirring is continued for an additional h. The precipitate is filtered off and the filtrate is evaporated to dryness at 35C (0.01 mm) (bath temperature). The residue is dissolved in THF
and filtered in a drybox under nitrogen. Diethyl ether is added to the solution and the precipitate is filtered and collected under nitrogen. The collected solid is fur~
ther purified by precipitation from THF with diethyl ether.
Anal. Calcd for (C13H17N3O2)n Found: C,62.69; H,7.64; N,14.54.

About 15mg of the abo~e prepared polymer (5.Omg) and the C2Br2C14 acceptor, lmg, are added to 29~1 THF and films are spun (2500 RPM) on a photoresist spinner. After ex-posure to X-rays as in the above examples, good images are obtained by use of methyl ethyl ketone developer sol-vent. No bakiny was required.

Polyphenoxytetrathiafulvalene About 15 mg of polyphenoxytetrathiafulvalene and 1.0 mg of C2Br2C14 are added to 29~1 THF and films are spun (2500 RPM) on a photoresist spinner. After exposure to X-rays as in the above examples, good images are obtained by use of methyl ethyl ketone developer sol-vent. No baking was required.

TABLE I
AlK~ X-Ray Resist Sensitivity (mj/cm ) Resolution PMMA** 1000 .02 POSITIVE PBS** 80 <1 RESISTS FBM** 30 <1 Methyl 20 >1~*
Acrylate NEGATIVE PGMA-EA** 5 >1~*
RESISTS Polysty- 40 ~0.2 rene-TTF**
*Materials are severely limited by swelling.
** PMMA - Poly(methyl methacrylate) PBS - Poly ~butene-l-sulfone) FBM - Poly (fluoro butyl methacrylate) PGMA-EA - Poly (glycidyl methacrylate ethyl acrylate copolymer) After X-ray exposure the polymer Eilms are readily removed by washing with a DMF solution which contained a few drops of the reducing agent hydrazine. Because YO9-79-0~0 this works by reducing the oxidized films, it is likely that other reducing agents (and solvents) can similarly be used.

Other functionalized polymers, e.g., poly~epichlorohydrin), poly(halophosphazenes), poly(acrylic chloride) and copolymers of the same were reacted with donors listed above. The resultant electroactive polymers were treated as in Examples 1-5 above and provided gooa images when exposed to X-ray radiation.

Claims (59)

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:
1. A method for producing negative resist images including the steps of:
(a) coating the film of a donor polymer-doped halocarbon charge transfer complex on a substrate, (b) exposing said film to X-ray radiation and thereafter (c) developing said exposed film in a suitable solvent.
2. A method according to claim 1 wherein said donor polymer is comprised of a polymer backbone and a donor molecule bonded thereto.
3. A method according to claim 1 wherein said donor polymer is comprised of a polymer backbone and a donor molecule bonded thereto and wherein said polymer backbone is selected from the group consisting of polyglutamic acid polyvinyl chloride polyepichlorohydrin, poly(.alpha.halophosphazenes) polyacrylic chloride and polystyrene and polyvinylbenzlchloxide said donor molecule is selected from the group consisting of tetrathiafulvalenes and its derivatives, amines having the formula R-NH2 where R can be an alkyl and an aryl group, pyrazolines, tetrathiatetracene, ferrocene and phenothiazine.
4. A method according to claim 2 wherein said polymer backbone is polyvinylbenzychloride having a tetrathiafulvalene as said donor molecule bonded thereto.
5. A method according to claim 2 wherein said polymer backbone is polyvinylbenzylchloride having a ferrocene as said donor molecule bonded thereto.
6. A method according to claim 2 wherein said polymer backbone is polyvinylbenzylchloride having a pyrazoline as said donor molecule bonded thereto.
7. A method according to claim 2 wherein said polymer backbone is polyvinylbenzylchloride having a dithiadiaselenafulvalene as said donor molecule bonded thereto.
8. A method according to claim 2 wherein said polymer backbone is polyvinylbenzylchloride having a phenothiazine as said donor molecule bonded thereto.
9. A method according to claim 2 wherein said polymer backbone is polyvinylbenzylchloride having an amine having the formula R NH2 where R is selected from an alkyl and an aryl group as said donor molecule bonded thereto.
10. A method according to claim 2 wherein said polymer backbone is polyvinylbenzylchloride having a N,N-dimethyl-p-phenylenediamine as said donor molecule bonded thereto.
11. A method according to claim 2 wherein said polymer backbone is polyvinylbenzylchloride having a tetrathiatetracene as said donor molecule bonded thereto.
12. A method according to claim 2 wherein said polymer backbone is glutamic acid having a tetrathiafulvalene as said donor molecule bonded thereto.
13. A method according to claim 2 wherein said polymer backbone is glutamic acid having a ferrocene as said donor molecule bonded thereto.
14. A method according to claim 2 wherein said polymer backbone is glutamic acid having a pyrazoline as said donor molecule bonded thereto.
15. A method according to claim 2 wherein said polymer backbone is glutamic acid having a dithiadiaselenafulvalene as said donor molecule bonded thereto.
16. A method according to claim 2 wherein said polymer backbone is glutamic acid having a phenothiazine as said donor molecule bonded thereto.
17. A method according to claim 2 wherein said polymer backbone is glutamic acid having an amine having the formula R-NH2 where R is selected from an alkyl and an aryl group as said donor molecule bonded thereto.
18. A method according to claim 2 wherein said polymer backbone is glutamic acid having a N,N-dimethyl-p-phenylenediamine as said donor molecule bonded thereto.
19. A method according to claim 2 wherein said polymer backbone is glutamic acid having a tetrathiatetracene as said donor molecule bonded thereto.
20. A method according to claim 2 wherein said polymer backbone is polyvinylchloride having a tetrathiafulvalene as said donor molecule bonded thereto.
21. A method according to claim 2 wherein said polymer backbone is polyvinylchloride having a ferrocene as said donor molecule bonded thereto.
22. A method according to claim 2 wherein said polymer backbone is polyvinylchloride having a pyrazoline as said donor molecule bonded thereto.
23. A method according to claim 2 wherein said polymer backbone is polyvinylchloride having a dithiadiaselenafulvalene as said donor molecule bonded thereto.
24. A method according to claim 2 wherein said polymer backbone is polyvinylchloride having a phenothiazine as said donor molecule bonded thereto.
25. A method according to claim 2 wherein said polymer backbone is polyvinylchloride having an amine having the formula R-NH2 where R is selected from an alkyl and an aryl group as said donor molecule bonded thereto.
26. A method according to claim 2 wherein said polymer backbone is polyvinylchloride having a N,N-dimethyl-p-phenylenediamine as said donor molecule bonded thereto.
27. A method according to claim 2 wherein said polymer backbone is polyvinylchloride having a tetrathiatetracene as said donor molecule bonded thereto.
28. A method according to claim 2 wherein said polymer backbone is polyepichlorohydrin having a tetrathiafulvalene as said donor molecule bonded thereto.
29. A method according to claim 2 wherein said polymer backbone is polyepichlorohydrin having a ferrocene as said donor molecule bonded thereto.
30. A method according to claim 2 wherein said polymer backbone is polyepichlorohydrin having a pyrazoline as said donor molecule bonded thereto.
31. A method according to claim 2 wherein said polymer backbone is polyepichlorohydrin having a dithiadiaselenafulvalene as said donor molecule bonded thereto.
32. A method according to claim 2 wherein said polymer backbone is polyepichlorohydrin having a phenothiozine as said donor molecule bonded thereto.
33. A method according to claim 2 wherein said polymer backbone is polyepichlorohydrin having an amine having the formulae R-NH2 where R is selected from alkyl and an aryl group as said donor molecule bonded thereto.
34. A method according to claim 2 wherein said polymer backbone is polyepichlorohydrin having a N,N-dimethyl-p-phenylenediamine as said donor molecule bonded thereto.
35. A method according to claim 2 wherein said polymer backbone is polyepichlorohydrin having a tetrathiatetracene as said donor molecule bonded thereto.
36. A method according to claim 2 wherein said polymer backbone is poly(.alpha.halophosphazenes3 having a tetrathiafulvalene as said donor molecule bonded thereto.
37. A method according to claim 2 wherein said polymer backbone is poly(.alpha.halophosphazenes) having a ferrocene as said donor molecule bonded thereto.
38. A method according to claim 2 wherein said polymer backbone is poly(.alpha.halophosphazenes) having a pyrazoline as said donor molecule bonded thereto.
39. A method according to claim 2 wherein said polymer backbone is poly(.alpha.halophosphazenes) having a dithiadiaselenafulvalene as said donor molecule bonded thereto.
40. A method according to claim 2 wherein said polymer backbone is poly(.alpha.halophosphazenes) having a phenothiazine as said donor molecule bonded thereto.
41. A method according to claim 2 wherein said polymer backbone is poly(.alpha.halophosphazenes) having an amine having the formula R-NH2 where R is selected from an alkyl and an aryl group as said donor molecule bonded thereto.
42. A method according to claim 2 wherein said polymer backbone is poly(.alpha.halophosphazenes) having a N,N-dimethyl-p-phenylenediamine as said donor molecule bonded thereto.
43. A method according to claim 2 wherein said polymer backbone is poly(.alpha.halophosphazenes) having a tetrathiatetracene as said donor molecule bonded thereto.
44. A method according to claim 2 wherein said polymer backbone is polyacrylic chloride having a tetrathiafulvalene as said donor molecule bonded thereto.
45. A method according to claim 2 wherein said polymer backbone is polyacrylic chloride having a ferrocene as said donor molecule bonded thereto.
46. A method according to claim 2 wherein said polymer backbone is polyacrylic chloride having a pyrazoline as said donor molecule bonded thereto.
47. A method according to claim 2 wherein said polymer backbone is polyacrylic chloride having a dithiadiaselenafulvalene as said donor molecule bonded thereto.
48. A method according to claim 2 wherein said polymer backbone is polyacrylic chloride having a phenothiazine as said donor molecule bonded thereto.
49. A method according to claim 2 wherein said polymer backbone is polyacrylic chloride having an amine having the formulae R-NH2 where R is selected from alkyl and an aryl group as said donor molecule bonded thereto.
50. A method according to claim 2 wherein said polymer bac]cbone is polyacrylic chloride having a N,N-dimethyl-p-phenylenediamine as said donor molecule bonded thereto.
51. A method according to claim 2 wherein said polymer backbone is polyacrylic chloride having a tetrathiatetracene as said donor molecule bonded thereto.
52. A method according to claim 2 wherein said polymer backbone is polystyrene having a tetrathiafulvalene as said donor molecule bonded thereto.
53. A method according to claim 2 wherein said polymer backbone is polystyrene having a ferrocene as said donor molecule bonded thereto.
54. A method according to claim 2 wherein said polymer backbone is polystyrene having a pyrazoline as said donor molecule bonded thereto.
55. A method according to claim 2 wherein said polymer backbone is polystyrene having a dithiadiaselenafulvalene as said donor molecule bonded thereto.
56. A method according to claim 2 wherein said polymer backbone is polystyrene having a phenothiazine as said donor molecule bonded thereto.
57. A method according to claim 2 wherein said polymer backbone is polystyrene having an amine having the formulae R-NH2 where R is selected from alkyl and an aryl group as said donor molecule bonded thereto.
58. A method according to claim 2 wherein said polymer backbone is polystyrene having a N,N-dimethyl-p-phenylenediamine as said donor molecule bonded thereto.
59. A method according to claim 2 wherein said polymer backbone is polystyrene having a tetrathiatracene as said donor molecule bonded thereto.
CA000358898A 1979-10-10 1980-08-25 Class of x-ray resists based on donor polymer-doped halocarbon acceptor transfer complexes Expired CA1161685A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5047445A (en) * 1988-06-20 1991-09-10 Victor Company Of Japan, Ltd. Electroconductive polymeric material

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61125019A (en) * 1984-11-16 1986-06-12 インタ−ナショナル ビジネス マシ−ンズ コ−ポレ−ション Manufacture of ic and photoconductive photoresist composite used therefor
JP5819810B2 (en) * 2012-12-18 2015-11-24 信越化学工業株式会社 Negative resist material and pattern forming method using the same

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5047445A (en) * 1988-06-20 1991-09-10 Victor Company Of Japan, Ltd. Electroconductive polymeric material

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JPS5662247A (en) 1981-05-28
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AU6298380A (en) 1981-04-16

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