CA1163671A - Class of e-beam resists based on donor polymer-doped halocarbon acceptor transfer complexes - Google Patents
Class of e-beam resists based on donor polymer-doped halocarbon acceptor transfer complexesInfo
- Publication number
- CA1163671A CA1163671A CA000358901A CA358901A CA1163671A CA 1163671 A CA1163671 A CA 1163671A CA 000358901 A CA000358901 A CA 000358901A CA 358901 A CA358901 A CA 358901A CA 1163671 A CA1163671 A CA 1163671A
- Authority
- CA
- Canada
- Prior art keywords
- polymer backbone
- donor molecule
- molecule bonded
- donor
- bonded
- 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
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Abstract A new class of E-beam resists is described. The resists are donor polymer-doped halocarbon acceptor transfer complexes. They are prepared from known polymeric back-bones such as polyvinylchloride, polyglutamic acid, polyvinylbenzylchloxide, polyepichlorohydrin, poly(ahalo-phosphazenes), polyacrylic chloride, polystyrene and the like; and donor molecules such as tetrathiafulvalenes, tetraselenafulvalenes, dithiadiselenafulvalene, ferro-cenes, 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
NEW CLASS OF E-~EAM RESISTS BASED ON DONOR
POLYMER-DOPED HALOCARBON ACCEPTOR
TRANSFER COMPLEXES
BACKGRO~ND OF THE INVENTION
Field of the Invention The invention lies in the field of E-beam resist compositions and the~production of patterned thin film layers therefrom~.
Prior Art The prior art is replete with radiation sensitive materials as resists and with their use in pattern formation Ln the fabrication of micro-electronic~devices. In the prior art, pattern formation in these materials is dependent upon di~ferential solubility between irradiated and unirradiated~regions. These solubility changes ar~e~produced by either bon~breaking, (chain scissioD) or bond formatlon (chain crosslinking) in polymeric sy~tems.~ This occurs in the presence ; 20 ~ of actinic~radLation,~ E-beam radiation or X-ray radiati;on.
yo979-~054 ..
67i 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; 3,769,023;
3,820,993; 3,895,954; 3,988,152 and 3,916,036. The resists disclosed in the above references are sensitive to either actinic or electron beam radiation. The prime need for the halocarbon in these resists are for the generation of free radicals to initiate polymerization.
More recently there nas been developed a new class of E-beam resist materials based on 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 ~esists Based On 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.
SUM~RY OF THE INVENTION
What has been dlscovered here are novel E-beam negative resists which can be broadly classified as donor polymer-doped halocarbon charge transfer complexes. More specifically, the materials comprise a polymer backbone or skeleton having bonded thereto electroactive molecules.
These electroactive polymer species are doped with a halocarbon.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 shows graphically the relationship between the exposure dose and the normalized thickness of a TTF resist exposed on a silicon substrate.
FIG. 2A and 2B show E-beam exposed patterns via scanning electron microscopy.
DESCRIPTION OF THE INVENTION
The present invention teaches novel E-beam 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* Techn cal 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 wîth the functional groups of donor molecules. Polymers which can be used, include polystyrene, a copolymer of polystyrene and chloromethylated styrene, e.g~, *Registered Trade Mark Of Internat.ional Business Machines Corporation r~
..
6~1 ~ ~CH2CR
[(cH2-cH)x (CH2-CH)~-x ]n where the value of X is varied (O<x~l), so that the number of donor molecules per chain and their dis~ance 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 (C IH2)2 ~, COOH
., , polyvinyl chloride [-CH2 - C~ H ~n . C~
.
~ polyepichlorohydrin , ~ ~ :
.
[~--C H 2--C H--O--]
;CH2 I
C~
Y0979-05~
., `. : :
~; : -` `` 1163671 poly(ahalo phosphazenes) X R
_ ~N-p _ n poly(acrylic chloride) ~CH -CH ~
COOCQ
and the like.
The donor molecules that can be used in this invention are those which can be characterized as having the following specific molecular properties:
ta) Those that are capable of electron oxidation to a cation.
tb) Have an oxidation potential of from about 0.lV
to about lV measured against a standard calomel electrode:
(c) those that photoionize in the presence of a halocar~o~; and (d) which have a functional group which when reacted with a polymer support will be bonded thereto.
Functional groups contemplated by the present invention include hydroxyl, phenoxy, carboxyl, amino groups and the like.
A wide variety of ~ donor molecules are expected to be active in polymeric form as negative resist materials~
::: : : :
:~ , :: :
;~ ~0979-054 .
`~ `` 1163671 This invention may ~e effected by usinq donors of the empirical formula C6H~X4R4 and having the structural formula X ~
where X=~, ~, Se and Te or any coMbination thereof.
The 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 connects Rl with R2 and R3 with R4, e.g. Some specific fulvalene compositions include tetrathiafulvalene (TTF), its derivatives and Se analogs (TSeF) and its derivatives. For example, tetrathiafulvalenecarboxylic acid (TTFCO2H), tetraselenafulvalenecarboxylic, (hydroxymethyl)-tetrathiafulvalene (TTFCH2OH), hydroxymethyl-tetraselenafulvalene (TSeFCH2OH), (p-hydroxyphenyl)-tetrathiafulvalene (TTFC6H4OH), (p-hydroxyphenyl)-tetraselenafulvalene ~TSeFC6H4OH), (p-aminophenyl)-tetrathiafulvalene (TTFC6H4NH2), tp-carboxyphenyl)-tetrathiafulvalene`(TTFC6~.4CO~-i), pheno::y (TTF~.
C~ <xx) .
The fol}owing fused rings, such as cyclopentene, cyclohexene, benzene, furan, thiophene, dihydrofuran 25~ and dihydrothiophene, and derivatives thereof can be used. In addition, tetrathiatetracene compounds, .
e.g.
S--S
:~ S S
yog79-054 : ~ ,, . ' :
. .~
`-`` 116~67~
and their derivatives are also sui.table ~or the purpose of this lnvention. In general, organic ~-electron donors having low ionization potentials (<7.5eV)2 can be used.
Additionally, the following compositions are contemplated by this invention;
~mines R-NH2, R=Alkyl, Ar~l Pyrazolines ~5~
~3 Pyrazolines of part.icular importance include 1,3-di-(p-methoxyphenyl)-5-(p-hydroxyphenyl)_~2_ pyrazoline, 1, 5-di-(p-methoxyphenyl)-3-(p-hydroxyphenyl)_~2_ pyrazoline, 3, 5-di-(p-methoxyphenyl)-l-(p-hydroxyphenyl)-~2-pyrazoline, l, 3-di-(p-methoxyphenyl)-5-(p-carboxyphenyl)_~2_ pyrazoline, l, 5-di-(p-methoxyphenyl)-3-~p-carboxyphenyl)-~2-pyrazoline,3, 5-di-(p-methoxyphenyl)-l-(p-carboxyphenyl)-~ -pyrazoline, l, 3-di-~p-methoxyphenyl)-5-(p-aminophenyl)-~2-pyrazoline, l, 5-di(phenyl)-3-(p-aminophenyl)-A2-pyrazoline, l-(p-hydroxyphenyl)-3-(p-methoxystyryl)-5-(p-methoxyphenyl)-~2-pyrazoline, l-(p-hydroxyphenyl)-3~(p-diethylaminostyryl)-5-(p-diethylaminophenyl)-Q -pyrazoline, .
~J 6367i 1 Ferrocene ~1 . .
m - m = Fe, etc.
Phenothiazine ~ ~3 [(n -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 a~oms.
(b) Has high electron affinity to accept electron from donor species (0-2eV).
:
(c) Forms anionic species.
Typical halocarbon acceptors which can be used are selected rom CC14, CBr4~ CI4~ C2 C16' C2 C12 4' 3 4 4
POLYMER-DOPED HALOCARBON ACCEPTOR
TRANSFER COMPLEXES
BACKGRO~ND OF THE INVENTION
Field of the Invention The invention lies in the field of E-beam resist compositions and the~production of patterned thin film layers therefrom~.
Prior Art The prior art is replete with radiation sensitive materials as resists and with their use in pattern formation Ln the fabrication of micro-electronic~devices. In the prior art, pattern formation in these materials is dependent upon di~ferential solubility between irradiated and unirradiated~regions. These solubility changes ar~e~produced by either bon~breaking, (chain scissioD) or bond formatlon (chain crosslinking) in polymeric sy~tems.~ This occurs in the presence ; 20 ~ of actinic~radLation,~ E-beam radiation or X-ray radiati;on.
yo979-~054 ..
67i 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; 3,769,023;
3,820,993; 3,895,954; 3,988,152 and 3,916,036. The resists disclosed in the above references are sensitive to either actinic or electron beam radiation. The prime need for the halocarbon in these resists are for the generation of free radicals to initiate polymerization.
More recently there nas been developed a new class of E-beam resist materials based on 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 ~esists Based On 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.
SUM~RY OF THE INVENTION
What has been dlscovered here are novel E-beam negative resists which can be broadly classified as donor polymer-doped halocarbon charge transfer complexes. More specifically, the materials comprise a polymer backbone or skeleton having bonded thereto electroactive molecules.
These electroactive polymer species are doped with a halocarbon.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 shows graphically the relationship between the exposure dose and the normalized thickness of a TTF resist exposed on a silicon substrate.
FIG. 2A and 2B show E-beam exposed patterns via scanning electron microscopy.
DESCRIPTION OF THE INVENTION
The present invention teaches novel E-beam 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* Techn cal 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 wîth the functional groups of donor molecules. Polymers which can be used, include polystyrene, a copolymer of polystyrene and chloromethylated styrene, e.g~, *Registered Trade Mark Of Internat.ional Business Machines Corporation r~
..
6~1 ~ ~CH2CR
[(cH2-cH)x (CH2-CH)~-x ]n where the value of X is varied (O<x~l), so that the number of donor molecules per chain and their dis~ance 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 (C IH2)2 ~, COOH
., , polyvinyl chloride [-CH2 - C~ H ~n . C~
.
~ polyepichlorohydrin , ~ ~ :
.
[~--C H 2--C H--O--]
;CH2 I
C~
Y0979-05~
., `. : :
~; : -` `` 1163671 poly(ahalo phosphazenes) X R
_ ~N-p _ n poly(acrylic chloride) ~CH -CH ~
COOCQ
and the like.
The donor molecules that can be used in this invention are those which can be characterized as having the following specific molecular properties:
ta) Those that are capable of electron oxidation to a cation.
tb) Have an oxidation potential of from about 0.lV
to about lV measured against a standard calomel electrode:
(c) those that photoionize in the presence of a halocar~o~; and (d) which have a functional group which when reacted with a polymer support will be bonded thereto.
Functional groups contemplated by the present invention include hydroxyl, phenoxy, carboxyl, amino groups and the like.
A wide variety of ~ donor molecules are expected to be active in polymeric form as negative resist materials~
::: : : :
:~ , :: :
;~ ~0979-054 .
`~ `` 1163671 This invention may ~e effected by usinq donors of the empirical formula C6H~X4R4 and having the structural formula X ~
where X=~, ~, Se and Te or any coMbination thereof.
The 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 connects Rl with R2 and R3 with R4, e.g. Some specific fulvalene compositions include tetrathiafulvalene (TTF), its derivatives and Se analogs (TSeF) and its derivatives. For example, tetrathiafulvalenecarboxylic acid (TTFCO2H), tetraselenafulvalenecarboxylic, (hydroxymethyl)-tetrathiafulvalene (TTFCH2OH), hydroxymethyl-tetraselenafulvalene (TSeFCH2OH), (p-hydroxyphenyl)-tetrathiafulvalene (TTFC6H4OH), (p-hydroxyphenyl)-tetraselenafulvalene ~TSeFC6H4OH), (p-aminophenyl)-tetrathiafulvalene (TTFC6H4NH2), tp-carboxyphenyl)-tetrathiafulvalene`(TTFC6~.4CO~-i), pheno::y (TTF~.
C~ <xx) .
The fol}owing fused rings, such as cyclopentene, cyclohexene, benzene, furan, thiophene, dihydrofuran 25~ and dihydrothiophene, and derivatives thereof can be used. In addition, tetrathiatetracene compounds, .
e.g.
S--S
:~ S S
yog79-054 : ~ ,, . ' :
. .~
`-`` 116~67~
and their derivatives are also sui.table ~or the purpose of this lnvention. In general, organic ~-electron donors having low ionization potentials (<7.5eV)2 can be used.
Additionally, the following compositions are contemplated by this invention;
~mines R-NH2, R=Alkyl, Ar~l Pyrazolines ~5~
~3 Pyrazolines of part.icular importance include 1,3-di-(p-methoxyphenyl)-5-(p-hydroxyphenyl)_~2_ pyrazoline, 1, 5-di-(p-methoxyphenyl)-3-(p-hydroxyphenyl)_~2_ pyrazoline, 3, 5-di-(p-methoxyphenyl)-l-(p-hydroxyphenyl)-~2-pyrazoline, l, 3-di-(p-methoxyphenyl)-5-(p-carboxyphenyl)_~2_ pyrazoline, l, 5-di-(p-methoxyphenyl)-3-~p-carboxyphenyl)-~2-pyrazoline,3, 5-di-(p-methoxyphenyl)-l-(p-carboxyphenyl)-~ -pyrazoline, l, 3-di-~p-methoxyphenyl)-5-(p-aminophenyl)-~2-pyrazoline, l, 5-di(phenyl)-3-(p-aminophenyl)-A2-pyrazoline, l-(p-hydroxyphenyl)-3-(p-methoxystyryl)-5-(p-methoxyphenyl)-~2-pyrazoline, l-(p-hydroxyphenyl)-3~(p-diethylaminostyryl)-5-(p-diethylaminophenyl)-Q -pyrazoline, .
~J 6367i 1 Ferrocene ~1 . .
m - m = Fe, etc.
Phenothiazine ~ ~3 [(n -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 a~oms.
(b) Has high electron affinity to accept electron from donor species (0-2eV).
:
(c) Forms anionic species.
Typical halocarbon acceptors which can be used are selected rom CC14, CBr4~ CI4~ C2 C16' C2 C12 4' 3 4 4
2 2 4~ ~H2C14, C2Br6, C3C18, Cl C C13, CHBr CHCl CH2C12 and the like.
The halocarbon agent may be present in amounts ranging from 0.01 to lO times the concentration of the donor moiety.
yo9-79-054 1~63671 There are two basic kinds of synthetic procedures for covalently attaching the donor molecules to the polymer resin. In equation (l), ~ CH2x~ D-y ~- ~ D
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 (D-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 alternate method, (i.e. reactions 2-4), the desired electroactive molecule is synthesized from polymer precursors directly on the resin.
Thus, functionalized electroactive species are not required; however, multiple polymer reactions become necessary.
O
C~S~ ~ CH2--C~S~!
~ CH2O C ~ S ~ ¢ S ~ E~3N ~ CH2O-C-TTF
`" llW67~
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 which can be used for film coating are toluene, chloroform, methylene chloride, cyclopentanone, tetrahydrofuran, methyl ethyl ketone etc.
The present inventive resist compositions are exposed to E-beam radiation.
Exposures were performed in a vacuum of about 10 6 torr on a scanning E-beam system at 20 KV beam voltage. The charge density is in the range of about lxlO 6 C/cm2 to about 50xlO 6 C/cm2.
More specifically, this invention concerns new compositions of matter which function in a novel resist process when irradiated by E-beams. For example, films of a polymeric TTF materials can be spin cast from a solution contain-ing a halocarbon acceptor, such as CBr4. Under these conditions the resulting polymer film contains CBr4 and becomes sensitive to radiation. When X-rays are used to irradiate these films through appropriate masks, only the unexposed areas can be removed from the underlying substrate by washing with a non-polar solvent. This nega-tive resist process is a novel one and unrelated to those suggested earlier for polymers whose solubility decreases upon exposure to radiation because of radia-tion induced crosslinking reactions.
llW671 It is suggested that these resists operate by means of 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 well known to occur in monomeric TTF, in solution U. S. Patent No. 4,036,648, where the halide salt produced is insoluble in non-polar solvents. This new mechanism for lithographic action has been established in the following ways.
Using visible-near ir spectrophotometry, the TTF
ions postulated in the above reaction 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. Torrance et al entitled "Optical Properties of the Radical Cation Tetrathiafulvalenium in its Mixed-Valence and Monovalence Halide Salts", Phys. Rev. B, 19, 730 (1979). Additional predictions of the suggested mechanism have also been observed. For instance, it would be expected that polymer films containing no halocarbon present would be much less sensitive to incident radiation.
Confirming this point it has been observed that irradiation of the undoped TTF polymer films gave no lithographic images when subjected to the same , ~ incident radiation as in the case of doped films.
~: .
~ ~ .
W67i 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) Drocess 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 (DMF).
However, when the chemical reducing agent hydrazine is added to the DMF solution it was observed that the exposed polymer film 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 be 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 2S present has been observed for a large number of donors in fluid solution. If the postulated 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.
. J
. .
`" ` il636~1 A prime disadvantage of previous negative resist materials ar~ the inherently low resolution of the patterns obtainable. As discussed earlier, negative resists typically operate by means of a radiation-induced crosslinking process. Although the crosslinked polymer that remains cannot be dissolved in a developer solvent, penetration of the solvent into the polymer causes swelling of the ~olymer chains since many of the development sol~ents 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 from the polymer matrix. Thus solvent cannot penetrate into the exposed polymer mass and cause swelling.
EXAMPLES
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 or scope thereof.
` `` ~163671 E~IPLE 1 Poly (vinylcarboxytetrathiaf~llvalene) Poly(vinylbenzylchloride), prepared from the monomer vinylbenzylchloride, 0.275g, and the cesium salt of tetrathiafulvalene carboxylic acid, 0.750mg, is added to 75ml of a DMF solvent and stirred at 75C for 24 hours. The solution is concentrated and the resultant polymer is isolated by precipitation into a rapidly stirred HzO solution~ Repeated precipitations from THF/H2O gave a dark brown solid. Anal- calc d for Cls 1 Hl1.653.5 l.7 C10.13 9 9t 7S4H3O2~o~87(cl)o 131 C=53.81, S=33.0g, Cl=0.14. Found C,53.74; S,32.96; Cl,0.23.
Polymer films are prepared by mixing 4.7mg of the polymer with 1 mg of C2~r2C14 which is added to 20~1 of cyclopentanone. The films are spin coated at 2S00 RPM on a photoresist spinner. No baking is required in order to obtain good images. Solvents which can be used as developers include tetrahydrofuran cyclopentanone, diglyme, methylene chloride, chloroform and mixtures thereof.
Several poly (TTF) films are prepared in this manner.
To determine the sensitivity of this resist, these films were exposed to E-beams with doses from 2-40xlO 6 C/cm2. The films were developed in 1:1 THF: Cyclopentanone and then the thickness of the remaining resist was determined.
From the resultin~
plot of normalized thickness remaining vs.
dose rate, see FIG. 1, it can be seen that the sensitvity of the material for 50~ thickness remaining is ~5 Coul/cm2. From data on other resist materials ~Table I), it can be seen that the present : ~ :
material is one of the most sensitive resist known.
Determination of Resolution of Resist:
An E-beam exposed pattern was studied via scanning electron microscopy ~see FIG. 2). These photographs show no evidence for the classical negative resist swelling behavior. All of the patterns are extremely well-formed, with parallel, vertical walls and showing no signs of pattern distortion. From the indicated scale, it is estimated that the present resist has a resolution of better than 20002.
Poly (vinylcarboxYferrocene) Poly (vinylbenzylchloride), (15 Omg) is reacted with the 360mg of cesium 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 precipitated into H20. Repeated precipitations (THF/H20) gave a light yellow solid.
Anal. calc'd for CgHg (C7 5H5 401~4 FeO 7) (Clo 3) C,69.9; Fe,13.4; Cl,4. Found C,67.62; Fe 12.11;
Cl,4.61.
.
Cesium salt of carboxyferrocene. ~lonocarboxyferrocene, 230 mg, is dissolved in ethanol. To this solution is added 5ml of H20 which contained 250mg CsHC03. ;
Using slight heating, and high vacuum, the solution was taken to dryness to produce the desired salt.
About 5.2mg of the so prepared polymer and about lmg of C2Br2C14, the acceptor compound are added to ` ```` ~16367~
26~1 of THF solvent and films are spun at 2500 RPM
on a Headway Photoresist Spinner. The films are exposed to E-beams having doses in the range 2 40 x 10 6 coul/cm2. Patterns are developed by one of the following solvents or mixtures thereof:
toluene, chloroform, methylene chloride, cyclopentanone, THF.
No pre or post exposure baking is required to obtain ~ood images.
Poly (vinylphenoxy-1,3-~p methoxyphenyl)-5-(p-hydroxyphenyl~-~2-pyrazoline):
The potassium salt of the pyrazoline is prepared by adding 374mg pyrazoline to 40 mg KH in dry THF.
After stirring for 30 minutes, 152mg of polyvinylbenzylchoride is added to this solution.
After refluxing for 4 days, the solvent volume was reduced and the polymer isolated following multiple reprecipitations from 50:5Q MeOH/H2O.
About 4.6mg of the polymer (4.6mg) and lmg of the C2Br2C14 acceptor, are added to 32ul of THF. Films were spun.'at 2500 RPM on a Headway Photoresist Spinner. After E-beam exposures as in the above examples, good images are obtained by developing in toluene: THF mixtures. No pre-or post exposure baking was required to obtain good images.
.
Poly[p-N,N-dimethylamino)-N-y-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 added. The solution is cooled to 0C and ' yo979-054 ~ ~ 17 11~6 ~
lg of DCC is added with stirring. Stirring is continued at 0C for 1 h and at room te~perature 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 tlle 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 further purified by precipitation from THF with diethyl ether. Anal. Calcd for (Cl3Hl7N3O2)n C 62-90;
H,6.85; ~,16.93. Found: C,62.69; H,7.64; N,14.54.
About 15mg of the above prepared polymer (5.Omg) and the C2Br2C14 acceptor, lmg, are added to 29ul THF and films are spun (2500 RPM) on a Photoresist Spinner. After exposure to E-beams as in the above examples, good images are obtained by use of methyl ethyl ketone developer solvent. No baking was required.
PolYphenoxytetrathiafulvalene About 15 mg of polyphenoxytetrathiafulvalene and 1.0 mg of C2Br2C14 are added to 29ul THF and films are spun (2500 RPM) on a photoresist spinner.
After exposure to E-beams as in the above examples, good images are obtained by use of methyl ethyl ketone developer solvent. No baking was re~uired.
`" ~`` i~6367i TABLE I
Resist E-Beam (20KV) 2 Resolution Dose 1~ Coul7cm P~MA* 80 1002 FBM* < 1 ~m PBS* 2 <.S um P(GMA-co-EA)* .3 1 ilm PS* 40 2000~~
~CA* 8 1 ~m * PMMA - Poly(methyl methacrylate) FBM - Poly (fluoro methacrylate~
PBS - Poly (butyl sulfone) P(GMA-co-EA) - Poly (qlycidyl methacrylate ethyl acrylate copolymer) PS - Polystyrene PCA - Polychloroacrylate After E-beams exposure the polymer films are readily removed by washing with a DMF solution which contained a few drops of the reducing agent hydrazine.
Because 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 l-S above and provided good imases when expo~ed to E-beam radiation.
:
: :
~ yo979-054 ~. . .
The halocarbon agent may be present in amounts ranging from 0.01 to lO times the concentration of the donor moiety.
yo9-79-054 1~63671 There are two basic kinds of synthetic procedures for covalently attaching the donor molecules to the polymer resin. In equation (l), ~ CH2x~ D-y ~- ~ D
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 (D-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 alternate method, (i.e. reactions 2-4), the desired electroactive molecule is synthesized from polymer precursors directly on the resin.
Thus, functionalized electroactive species are not required; however, multiple polymer reactions become necessary.
O
C~S~ ~ CH2--C~S~!
~ CH2O C ~ S ~ ¢ S ~ E~3N ~ CH2O-C-TTF
`" llW67~
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 which can be used for film coating are toluene, chloroform, methylene chloride, cyclopentanone, tetrahydrofuran, methyl ethyl ketone etc.
The present inventive resist compositions are exposed to E-beam radiation.
Exposures were performed in a vacuum of about 10 6 torr on a scanning E-beam system at 20 KV beam voltage. The charge density is in the range of about lxlO 6 C/cm2 to about 50xlO 6 C/cm2.
More specifically, this invention concerns new compositions of matter which function in a novel resist process when irradiated by E-beams. For example, films of a polymeric TTF materials can be spin cast from a solution contain-ing a halocarbon acceptor, such as CBr4. Under these conditions the resulting polymer film contains CBr4 and becomes sensitive to radiation. When X-rays are used to irradiate these films through appropriate masks, only the unexposed areas can be removed from the underlying substrate by washing with a non-polar solvent. This nega-tive resist process is a novel one and unrelated to those suggested earlier for polymers whose solubility decreases upon exposure to radiation because of radia-tion induced crosslinking reactions.
llW671 It is suggested that these resists operate by means of 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 well known to occur in monomeric TTF, in solution U. S. Patent No. 4,036,648, where the halide salt produced is insoluble in non-polar solvents. This new mechanism for lithographic action has been established in the following ways.
Using visible-near ir spectrophotometry, the TTF
ions postulated in the above reaction 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. Torrance et al entitled "Optical Properties of the Radical Cation Tetrathiafulvalenium in its Mixed-Valence and Monovalence Halide Salts", Phys. Rev. B, 19, 730 (1979). Additional predictions of the suggested mechanism have also been observed. For instance, it would be expected that polymer films containing no halocarbon present would be much less sensitive to incident radiation.
Confirming this point it has been observed that irradiation of the undoped TTF polymer films gave no lithographic images when subjected to the same , ~ incident radiation as in the case of doped films.
~: .
~ ~ .
W67i 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) Drocess 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 (DMF).
However, when the chemical reducing agent hydrazine is added to the DMF solution it was observed that the exposed polymer film 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 be 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 2S present has been observed for a large number of donors in fluid solution. If the postulated 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.
. J
. .
`" ` il636~1 A prime disadvantage of previous negative resist materials ar~ the inherently low resolution of the patterns obtainable. As discussed earlier, negative resists typically operate by means of a radiation-induced crosslinking process. Although the crosslinked polymer that remains cannot be dissolved in a developer solvent, penetration of the solvent into the polymer causes swelling of the ~olymer chains since many of the development sol~ents 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 from the polymer matrix. Thus solvent cannot penetrate into the exposed polymer mass and cause swelling.
EXAMPLES
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 or scope thereof.
` `` ~163671 E~IPLE 1 Poly (vinylcarboxytetrathiaf~llvalene) Poly(vinylbenzylchloride), prepared from the monomer vinylbenzylchloride, 0.275g, and the cesium salt of tetrathiafulvalene carboxylic acid, 0.750mg, is added to 75ml of a DMF solvent and stirred at 75C for 24 hours. The solution is concentrated and the resultant polymer is isolated by precipitation into a rapidly stirred HzO solution~ Repeated precipitations from THF/H2O gave a dark brown solid. Anal- calc d for Cls 1 Hl1.653.5 l.7 C10.13 9 9t 7S4H3O2~o~87(cl)o 131 C=53.81, S=33.0g, Cl=0.14. Found C,53.74; S,32.96; Cl,0.23.
Polymer films are prepared by mixing 4.7mg of the polymer with 1 mg of C2~r2C14 which is added to 20~1 of cyclopentanone. The films are spin coated at 2S00 RPM on a photoresist spinner. No baking is required in order to obtain good images. Solvents which can be used as developers include tetrahydrofuran cyclopentanone, diglyme, methylene chloride, chloroform and mixtures thereof.
Several poly (TTF) films are prepared in this manner.
To determine the sensitivity of this resist, these films were exposed to E-beams with doses from 2-40xlO 6 C/cm2. The films were developed in 1:1 THF: Cyclopentanone and then the thickness of the remaining resist was determined.
From the resultin~
plot of normalized thickness remaining vs.
dose rate, see FIG. 1, it can be seen that the sensitvity of the material for 50~ thickness remaining is ~5 Coul/cm2. From data on other resist materials ~Table I), it can be seen that the present : ~ :
material is one of the most sensitive resist known.
Determination of Resolution of Resist:
An E-beam exposed pattern was studied via scanning electron microscopy ~see FIG. 2). These photographs show no evidence for the classical negative resist swelling behavior. All of the patterns are extremely well-formed, with parallel, vertical walls and showing no signs of pattern distortion. From the indicated scale, it is estimated that the present resist has a resolution of better than 20002.
Poly (vinylcarboxYferrocene) Poly (vinylbenzylchloride), (15 Omg) is reacted with the 360mg of cesium 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 precipitated into H20. Repeated precipitations (THF/H20) gave a light yellow solid.
Anal. calc'd for CgHg (C7 5H5 401~4 FeO 7) (Clo 3) C,69.9; Fe,13.4; Cl,4. Found C,67.62; Fe 12.11;
Cl,4.61.
.
Cesium salt of carboxyferrocene. ~lonocarboxyferrocene, 230 mg, is dissolved in ethanol. To this solution is added 5ml of H20 which contained 250mg CsHC03. ;
Using slight heating, and high vacuum, the solution was taken to dryness to produce the desired salt.
About 5.2mg of the so prepared polymer and about lmg of C2Br2C14, the acceptor compound are added to ` ```` ~16367~
26~1 of THF solvent and films are spun at 2500 RPM
on a Headway Photoresist Spinner. The films are exposed to E-beams having doses in the range 2 40 x 10 6 coul/cm2. Patterns are developed by one of the following solvents or mixtures thereof:
toluene, chloroform, methylene chloride, cyclopentanone, THF.
No pre or post exposure baking is required to obtain ~ood images.
Poly (vinylphenoxy-1,3-~p methoxyphenyl)-5-(p-hydroxyphenyl~-~2-pyrazoline):
The potassium salt of the pyrazoline is prepared by adding 374mg pyrazoline to 40 mg KH in dry THF.
After stirring for 30 minutes, 152mg of polyvinylbenzylchoride is added to this solution.
After refluxing for 4 days, the solvent volume was reduced and the polymer isolated following multiple reprecipitations from 50:5Q MeOH/H2O.
About 4.6mg of the polymer (4.6mg) and lmg of the C2Br2C14 acceptor, are added to 32ul of THF. Films were spun.'at 2500 RPM on a Headway Photoresist Spinner. After E-beam exposures as in the above examples, good images are obtained by developing in toluene: THF mixtures. No pre-or post exposure baking was required to obtain good images.
.
Poly[p-N,N-dimethylamino)-N-y-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 added. The solution is cooled to 0C and ' yo979-054 ~ ~ 17 11~6 ~
lg of DCC is added with stirring. Stirring is continued at 0C for 1 h and at room te~perature 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 tlle 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 further purified by precipitation from THF with diethyl ether. Anal. Calcd for (Cl3Hl7N3O2)n C 62-90;
H,6.85; ~,16.93. Found: C,62.69; H,7.64; N,14.54.
About 15mg of the above prepared polymer (5.Omg) and the C2Br2C14 acceptor, lmg, are added to 29ul THF and films are spun (2500 RPM) on a Photoresist Spinner. After exposure to E-beams as in the above examples, good images are obtained by use of methyl ethyl ketone developer solvent. No baking was required.
PolYphenoxytetrathiafulvalene About 15 mg of polyphenoxytetrathiafulvalene and 1.0 mg of C2Br2C14 are added to 29ul THF and films are spun (2500 RPM) on a photoresist spinner.
After exposure to E-beams as in the above examples, good images are obtained by use of methyl ethyl ketone developer solvent. No baking was re~uired.
`" ~`` i~6367i TABLE I
Resist E-Beam (20KV) 2 Resolution Dose 1~ Coul7cm P~MA* 80 1002 FBM* < 1 ~m PBS* 2 <.S um P(GMA-co-EA)* .3 1 ilm PS* 40 2000~~
~CA* 8 1 ~m * PMMA - Poly(methyl methacrylate) FBM - Poly (fluoro methacrylate~
PBS - Poly (butyl sulfone) P(GMA-co-EA) - Poly (qlycidyl methacrylate ethyl acrylate copolymer) PS - Polystyrene PCA - Polychloroacrylate After E-beams exposure the polymer films are readily removed by washing with a DMF solution which contained a few drops of the reducing agent hydrazine.
Because 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 l-S above and provided good imases when expo~ed to E-beam radiation.
:
: :
~ yo979-054 ~. . .
Claims (59)
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 E-beam radiation and thereafter (c) developing said exposed film in a suitable solvent.
(a) coating the film of a donor polymer-doped halocarbon charge transfer complex on a substrate, (b) exposing said film to E-beam 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-NH 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.halophosphazenes) 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.
'2 4
'2 4
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 backbone 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.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US8349579A | 1979-10-10 | 1979-10-10 | |
| US083,495 | 1979-10-10 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1163671A true CA1163671A (en) | 1984-03-13 |
Family
ID=22178715
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000358901A Expired CA1163671A (en) | 1979-10-10 | 1980-08-25 | Class of e-beam resists based on donor polymer-doped halocarbon acceptor transfer complexes |
Country Status (2)
| Country | Link |
|---|---|
| AU (1) | AU539639B2 (en) |
| CA (1) | CA1163671A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113942146A (en) * | 2021-10-14 | 2022-01-18 | 董波 | Material separation and dust collection device for chlorinated polyethylene production |
-
1980
- 1980-08-25 CA CA000358901A patent/CA1163671A/en not_active Expired
- 1980-10-06 AU AU62981/80A patent/AU539639B2/en not_active Ceased
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113942146A (en) * | 2021-10-14 | 2022-01-18 | 董波 | Material separation and dust collection device for chlorinated polyethylene production |
| CN113942146B (en) * | 2021-10-14 | 2023-12-22 | 陕西开赛德新型材料科技有限公司 | Material separation and dust collection device for chlorinated polyethylene production |
Also Published As
| Publication number | Publication date |
|---|---|
| AU6298180A (en) | 1981-04-16 |
| AU539639B2 (en) | 1984-10-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP0102450B1 (en) | Resist compositions | |
| US5561030A (en) | Fabrication of electronically conducting polymeric patterns | |
| JP2929526B2 (en) | N-vinyl lactam derivative, its polymer, and photoresist containing the polymer | |
| US4054635A (en) | Copolymer of glycidyl methacrylate and allyl glycidyl ether | |
| US4054455A (en) | Article having a layer containing a copolymer of glycidyl methacrylate and allyl glycidyl ether | |
| US4548893A (en) | High resolution lithographic resist and method | |
| US4517276A (en) | Metal-containing organic photoresists | |
| CA1163671A (en) | Class of e-beam resists based on donor polymer-doped halocarbon acceptor transfer complexes | |
| US4346163A (en) | Resist for use in forming a positive pattern with a radiation and process for forming a positive pattern with radiation | |
| EP0027180B1 (en) | Photo, e-beam, and x-ray sensitive negative resists based on donor polymer-doped halocarbon acceptor transfer complexes and method for producing negative resist images | |
| CA1161685A (en) | Class of x-ray resists based on donor polymer-doped halocarbon acceptor transfer complexes | |
| US5998089A (en) | Photosensitive resin composition comprising fullerene | |
| CA1175990A (en) | Class of photo resists based on donor polymer-doped halocarbon acceptor transfer complexes | |
| JPH0766189B2 (en) | Resist material | |
| US4262083A (en) | Positive resist for electron beam and x-ray lithography and method of using same | |
| US4056393A (en) | Method of recording information using a copolymer of glycidyl methacrylate and allyl glycidyl ether | |
| US3779989A (en) | Light-sensitive polymers containing a phenyl-diarylcyclopropene moiety,their preparation and use | |
| JP2662141B2 (en) | Device manufacturing method | |
| US3341472A (en) | Photoconductors and method of making the same | |
| US4897336A (en) | Self-developing radiation sensitive resist with amorphous polymer having haloalkyl substitution derived from cycic ether | |
| US3849144A (en) | Light-sensitive compositions comprising polymers containing diarylcyclopropene moiety and process of using | |
| US4581318A (en) | N-alkynyl polyvinylpyridinium resists having electron and deep U.V. sensitivity | |
| US4054452A (en) | Method of imaging a layer containing copolymer of glycidyl methacrylate and allyl glycidyl ether | |
| JPS5975244A (en) | Radiation sensitive organic polymer material | |
| JPS5953837A (en) | Pattern forming material and pattern forming method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |