CA1161192A

CA1161192A - Negative-working polymers useful as electron beam resists

Info

Publication number: CA1161192A
Application number: CA000361322A
Authority: CA
Inventors: Zoilo C.H. Tan; Constantine C. Petropoulos; Frederick J. Rauner
Original assignee: Eastman Kodak Co
Current assignee: Eastman Kodak Co
Priority date: 1980-06-27
Filing date: 1980-10-01
Publication date: 1984-01-24
Also published as: DE3167592D1; EP0043116A2; JPS5752050A; JPS6248819B2; US4289842A; EP0043116B1; EP0043116A3

Abstract

Abstract .
Novel acrylate copolymer material function as electron-beam resists with enhanced sensitivity and enhanced plasma etch resistance. The method of using such materials as an electron-beam resist is also described.

Description

l 1 61 19~

NEGATIVE-WORKING POLYMERS USEFUL AS ELECTR.ON BEAM RESISTS
1) Field of the Invention ~ .
This inven~ion relate~ to ne~ati~e-working polymer~
suitable for exposure to electron beam~ to form ~ re~i~t.
Such resists are particularly useful in the m~nufacture of semiconductor devices.

2) Back~round of the Invention Electron-beam exposure device~ have been found to be a useful tool in providing controlled line expo~ure~ of sub-10 micron dimensions. Such dimension~ accompanied by ~ricttolerances, are essential to the production of integrated circuit chips. The procedure i~ to expose negative workin~
resists applied to suitable substrate6, to electron beams having widths of submicron dimen~ion~. After the re~iEt is 1~ developed, the substrate not protected by the resi~t i~
etched, usually by a chemicAl or plasma etching. Example~ of such procedures, including ehe expo~ure and development of the resist, sre described in J. Vac. Sci. Teehnol., Yol. 15, No. 3, pp. 960 964 (May/June 1979).
One of the difficulties with ~ch a procedure i5 the scarcity of useful negative-working resist~. No~. only must the resist demonstrate sensitivity to an electroll beam of conventional voltage, but it must al~o resis~ deorma~ion and dissolution by the etching process applied ~o ~he ~ub~trate 25 or base material, usually a semiconductorO More ~peci-fically, it is preferred that, for direct writing application the resist have a ~ensitivity of at least about 2.0 X 10 7 coulombs/cm2 at 10 keV, a submicron re~olution capability, ther~al stability, and a resistance to etching. Such re-30 quirements are particularly difficult to achieve in light ofthe fact that prior 6tudies have suggest~d that ~ensitivities in the 10 8 coulombs/cm2 range produce thermal in~tabil-ity.
A few acrylate copolymer~ have been de~cribed ~
35 uxeful elestron-beam re~i~ts. Poly(glycidyl methacrylate-co-ethyl acrylate) i8 mentioned in the afore~aid article in J.
Yac. Sci. Technol. However, it~ sen~itivity achieves the desired value of 2 X 10 7 coulomb~tcm2 at 10 keV, only ,~

1 :7 61 1 9 ?, at rela~ively high molecular weights. Furthermore, lt~
resistance to pla6m8 etching is not as good ~8 i~ de~ired.
An additional poly(acrylate) described ~ ~ensitive to electron-beam exposure is ~ copolymer of 2-hydrsxyethyl acrylate and saturated vinyls ~Uch ~S methyl ~ethacrylate ~nd butyl methacrylate. Examples ~re listed in Briti6h P~tent Specification 1,407,312, but as pain~s rather than ~s resists. Of interect is the fact that thi~ ps~ent discredits the hydroxyethyl methacryla~e homolog copolymer A6 being too insensitive to be useful.
Therefore, what is desired is a negative-working resist having a sensitivity to electron beams of ~t least 2 X 10-7 coulombs/cm2 at molecular weights les~ than 100,000, improved plasma etch resistance, and adequate sub-micron resolution capability.
SUMMARY OF THE INVENTION
The present invention advantageously features a neg-ative-working resist having the desired electron-beam ~ensi-tivity and improved pl~sma etch resistance noted above.
In a related feature of the inven~ion, ~I negative-working resist is provided that has, in addition to the above-noted sensitivity, enhanced thermal stability.
More specifically, in ~ccordance with oale ~speet of the invention there is provided a polymer having a negative-working electron sensitivity of at least 2 X 10 7 coulomb/cm2 when exposed to a 10 keV electron be~m, the polymer having recurring units with the structure R ~1 ~ CH2~C ~x ~ C~2-C ~y C-O . g:-O
O ` T
R2 ~3 ~H
wherein R and Rl are each independently hydrogen or m*thyl, R2 is ~CH2~n CHGCH2 or ~;

-3-n is 1, 2 or 3;
R3 is alkylene of from 1 to 3 c~rbon ~tom~;
T is -O- or -NH-, ~nd x and y are mole percents 6uch that 50 _ x < 95 5 ~ y < 50.
This polymer comprises the negative-working resist noted above, and can be applied to any suitable substrate as ~ pro-tective coating.
In ano~her a~pect of the invention, a ~ethod of ima~ewise hardening on a substrate, ~ layer of ~ resist comprising the polymer described above, ~OmpriSeB the steps of a) imagewise exposing the layer to electron bea~ radiation of an energy no greater than about 10 keV; and b) developing 15 the layer by washing it wi~h a solvent for the unexposed polymer.
Other features and advantages of the invention will become apparent upon reference to the following Description of the Preferred Embodiments.
DESCRIPTION OF THE PREFERRED EMBODIMEN"rS
The polymers of the invention ~re herein~lifter de-scribed primarily as materials useful as electron beam resists. These polymers are al60 useful as re6ists exposed to other forms of high energy radiation, such as x-ray 25 radiation.
It has been discvvered that both enhanced 6ensi-tivity and enhanced etch resistance are obtained by co-polymerizing an unsaturated monomer and a hydroxy alkyl monomer. The polymers of the invention have recurring units 30 of the structure set forth in the Summary. A subclass of polymers havin~ such structure includes those having the structure ~ *
t t ~ C~2~ CH2 C ~y 3~ C-~ C-O
O T
R4 ~3 CH C~2 OH

1 ~ 61 19 For ~his subclass, examples of useful R3 ~nd R4 groups include, individually, methylene, ethylene, n-propylene snd isopropylene.
Specific preferred examples of polymerg of this in-vention include poly[allyl meth~crylate-co-(2-hytroxyethyl methacrylate)]; poly[4-butenyl meth~crylate-co-(2~hydroxy-ethyl methacrylate)]; poly[3-norbornenyl methacrylste-co-(2-hydroxyethyl methacrylate; and poly(allyl ~ethacrylate~
co-2-hydroxypropylmethacrylamide).
Other comonomers can be included to form other re-curring units in the polymer of the invention, prov;ded that they are compatible--that is, that they do not interfere with the crosslinking of the polymer. Preferably, to insure maxi-mum sensitivity and etch resistance, x ~nd y to~ether com-prise at least 80 mole percent of the polymer. Most pref-erably x plus y totals 100 mole percent and y i6 between about 25 and 30 mole percent, as it has been ound tha~ such polymers, by reason of the increased ~ole percent of hydroxy groups present, have enhanced plasma etch resistance.
The polymers of the invention have electron-beam sensitivities that meet the ~bove-noted requirement of at least 2 X 10-7 coulombs~cm2. In several cases, they are much more sensitive than this. Such results are achieved for weight average molecular weights (hereinafter "Mw") tha~ ~re, in most cases, well below 100,000. Thus, on a per molecular weight basis, the polymers of the inven~ion comprise one of the most sensitive negative-working electron-beam resists available. Electron-beam sensitivities herein described were determined, as is conventional, by exposing iden~ical coat-3o ings to increased dosage values and measuring the amount of resist remaining in the exposed area after development. The sensitivity is that dosage requ;red to crosslink enough of the composition to retain 50% of the initial coating thick-ness.
The molecular weights of useful polymers of the in-vention can vary widely, as long as the polymer has 8 low enough viscosity in the solvent of choice to permit it to be ~ ~ 61 1~2 coated. It has been found that useful viscositie~ ~re gen-erally 0.3 inherent visco~fty or less, ~s mea~,ured in N,N-dimethylformamide. However, low molecular weight~ tend to reduce the elec~ron-beam 6ensitivi~y undeF,irably. Pref-erably, therefore~ the weight average molecular weight of thepolymer, as determined by gel permeation chromatography analysis, is be~ween about 20,000 and ~bout 200,000. ~o~t preferably, it i6 between ~bout 40,000 ~nd 50,000.
There is ~ome evidence that ~he disperf,ity of the 10 polymer, as measured by the ratio Mw/Mn where Mn is the num-ber average molecular weigh~, ~ffects inversely the re~olu-tion cspability of the polymer. Although thi~ i8 not con-sidered a critical factor, the most preferred example~ of the invention have a polydispersi~y value of 3.0 or le~s. The 15 polymers of the invention provide in gener~l a resolution of 0.3 ~m line per 1.0 ~m space, when expof,ed to elect~on be~ms as described.
The polymers of the invention are prepared by conventional synthesis techniques. It should however be 20 noted that dilute reaction conditions sre preferred to ~void undesirable crosslinking. The following preparatlons are illustrative. The amide monomer of ehe amide cop~lymer noted above can be prepared by Preparation No. 17 of Briti~h Patent Specification No. 1,463,816.
25 Preparation No. 1 ~2-f~
COOC~2 Q C~2 3 ~DO~C~H
~ 89, ~ - 14,7Cl~ 2.~1 A 3 liter reaction vessel was equipped with a magnetic ~tir-rer, heating mantle, reflux condenser, addition funnel, ~nd 35 nitrogen inlet. R solution of 100 g of allyl methacryate, 34.4 g of 2 hydroxyethyl methacrylate, ~nd 1.33 g of 2,2'-azobis(2-methyl propionitrile~ in 530 ml of 1,2 dichloro-11 61 l9Z
~, ethane (DCE) was added dropwise to 2 li~er~ of ~tirred,refluxing DCE under a nitrogen ~tmosphere in the ~fore-mentioned vessel. The reaction conditions were maintained for 6 hrs after completion of the addition. When cool, the reaction solution was concentrated to 650 ml under ~n aspirator~generated-vacuum without heating. The resulting solution was added dropwise to 8 liters of vigorously ~irred hexane whereupon the polymer precipitated. The ~olids were collected on a filter funnel, washed with fresh hexane and 10 dried in vacuo with no heat. 105 g yield.
Elemental analysis: calc C 63.8 H 7.90 O 28.3 found C 63.6 H 8.30 O 28.1 Thermogravimetric analysis: E~otherm @ 174C
Weight loss - 4% @ 68-134C; 0.5% @ 134-195C;
1544.5% @ 195-383C; 49% @ 383-471C
Preparation No. 2 2~ ~ 2-f ~ G2- ~ -COOCH2C~cH2 3 ~OOeB2~2 ~w ~ 76,180; ~ ~ 2~,7~0s B~n ~ 3,07 25 A 1 liter reaction vessel was equipped with a mechan;cal stirrer, addition funnel, reflux condensor, nitrogen inle~
and immersed in a 80C constant-temperature bath. A ~olution of 18.9 g of allyl methacrylate, 6.5 g of 2-hydroxyethyl methacrylate, and 50 mg of 2,2'-azobis(2~methyl propio-30 nitrile) in 100 ml of N,N-dimethylformamide (DMF) was added dropwise to 375 ml of stirred, refluxing DMF under a nitrogen atmosphere in the aforementioned vessel. Reaction conditions were maintained for 10 hrs. When cool, the reaction ~olu-tion was added dropwise to 5 liters of water whereupon the 35 polymer precipitsted. The solids were collected on a filter funnel, washed with fresh water and dried in vacuo without heating. 16.9 g yield.
Inherent viscosity, measured as (0.25 g/dl, was 0.11 in 1 6 ~ 2 1,2-dichloroethane, 0.13 in N,N-dimethyl-formamide.
Elemental analysiB: Calc C 6308 H 7.g 0 Z8.3 Found C 63.1 H 8~2 0 28.7 Preparation N~ 3 ~ 'R2 ~ C~2 10OD~C~2-~H-C~ 9 ~ ~ 60,~90s ~ ~ 17,~27~ n A solution of 100 g of allyl methacrylate, 11.5 g of 2-hydroxyethyl methacrylate, and 1.11 g of 2,2'-azobis(2-me~hyl propioni~rile) in 500 ml of DCE was added dropwi~e to 2 liters of stirred refluxing DCE under a nitrogen atmosphere 20 in a reaction vessel similar to that employed in Preparation No. 1. The reaction conditions were maintained overnight (18 hrs). When cool, 2 mg of hydroquinone was dissolved in he reaction solution. One-half of the solvent was removed under an aspirator-generator vacuum with minimal heating ~nd 579 ml 25 Of 2-ethoxyethyl acetate was added. The remaining DCE in the reaction solution was removed as before. A small sample of the resulting solution was added dropwise to sti~red ligroin to precipitate the polymer. The solids were collec~ed on a filter funnel, washed wi~h fresh ligroin, snd dried.
3o Elemental analysis: % allyl = 84 by carbon analysis Calc C 64.8 H 8.0 0 27.2 Found C 64.8 H 8.6 0 26.6 Inherent viscosity, measured as 25 gldl. was 0.09 in N,N-dimethylformamide.
As a resist, the polymers of the invention are l g 2 preferably coated onto the ~ub~trate that i~ to be etch~d.
The resist is then dried, imagewi~e expo~ed, ~nd developed to remove the unexposed portion6. Any suitable ~ubstr~te i~
useful. Particularly preferred examples include semi-conductors such as 6ilicon wafer~, chrome-clfld glazs, snd metals such as aluminum.
Conventional 601vents are useful for both the coat-ing step and the development s~ep. Preferred example~ of solvents useful for either proces~ step include 2-methoxy-ethyl acetate, 2-ethoxyethyl ~cetate, 2-ethoxyethanol, 2-butanone and mixture~ of these with 2-propanol or ethanol.
Conventional coating procedures are u~eful to apply the polymer to the substrate. Preferred ~re whirler or ~pin coating, brushing, doctor-blade coating, or hopper coating.
Further details of ~uch convent~onal procedures are de6cribed in Product Licensin~ Index, Vol. 92, Dec. 1971, Publicstion No. 9232, at p. 109.
The drying step is conveniently accompli~hed by bak-ing in an oven, optionally in a vacuum, for example ~t 90~C
for 30 minutes.
Optionally, a post-bake ~ep i~ included afeer ex-posure and development to enhance adhesion of the final resist coating to the areas to be protected, prior to etch-ing. Such treatment is conventional and requires no further discussion.
Etching of the underlying ~ubstrate i~ ~chieved by using a chemical ~olvent for the substrate, or by ~ pla~ma gas, both of which are conventional. Etch resistance is measured herein as the rate at ~hich the resist iB removed by the etchsnt, in A per minute, to reflect the fact that, for a given electron beam exposure level, the resist will have-a different starting thickne~s, depending on the polymer com-position.
Examples The following examples are included for a further illustration of the invention.
Example 1: Poly~allyl methacrylate-co-(2-hydroxyethyl - methacrylate)~ (75 25) Re~ist . 9 2 9 ~
A 20% solution of the polymer of Preparation No. 1 was spun-coated onto a chrome-clad gla~s ~ub~trate out of 2-ethoxyethyl acetate to provide a thicknes~ of 1 ~m dfter drying at 90C for 30 minutes. When exposed to ~n eleetron beam directed through baffle plates having 1/4 inch diameter holes to achieve uniform elec~ron intensity, at 10 keV, thi6 resist had a sensitivity of 1.1 X 10-7 coulo~bs/cm2.
Examples 2 and 3: Comparison With Other Polyacrylate Re~i~ts The procedure of Example 1 wa~ repeated using the 10 same polymer recurring units as tested in Example 1, except that the polymers were from two different bfltches of lower molecular weight, coated to produce the ~ame thickness. The weight average molecular weighes are indicated in Table I.
As a control, poly(allyl methacrylate-co-ethyl meth-15 acrylate)(75 25) similar to ~hat deseribed in U.S~ PatentNo. 3,376,138 was obtained, coated and tested. The &ensi-tivities are indicated in Table 1.
Table_I
Sensitivity 20 Example Polymer Mw (Coulombs/cm2) 2 poly[allyl methacrylate- 23,600 2 X 10 7 co-(2-hydroxyethyl meth-acrylate)] (75:25) 3 " 19,~19 1.~3 X 10-7 25 Control poly(allyl methacrylate- 22,000 5 X 10 7 co-ethyl methacrylate) (75:25) The results of Table I indicate that removing en-tirely the hydroxy group from the ethyl methacrylate comono-3 mer, all other factors being essentially equal, caused a ~ig-nificant detrimental reduction in 6ensitiv~ty.
Example 4: Demonstration of Improved ~tch Resistance The procedure of Example 1 was repeated using the 6ame polymer recurring units as te~ted in Example 1, except 35 that again the molecular weight was altered during the prep-aration of the polymer, ~s ~tated in Table II. In addition, after exposure at a dosage rate of at least 3 X 10 7 coulombs/cm2, the sample was post-baked at 170C for 30 1 3 ~ 2 minutes and plasma etched for 3 minutefi using a 93/4/3 mixture of CF4, 2 and ~2~ reBpectively at 1~ ~m pr~s-sure and 100 watts power, and 20 keV energy. The control was poly(glycidyl methacrylate-co-ethyl acrylste) S72 2~) 6imi-lar to the polymer identified in the aforesaid srticle in J.Vac. Sci. Technol. The resulting etch resiBtances are listed in Table II.
Table I
Etch Re~ist~nce Example Polymer Mw (A/min)

4 poly[allyl methacrylate- 48,700 175 co-(2-hydroxyethyl meth-acrylate)](75 25) 15 Control polytglycidyl meth- 192,000 350 acylate-co-ethyl acrylate)~72:28) obtained from KTIIMead Chemicals Inc.
20 The results of Table Il demonstrate that, for plasma etching, and at comparable molecular weights, the polymers of the in-vention tend to be superior to poly(glycidyl methacrylate eo-ethYl aCrylate) (72:28) because less resist is removed per minute.
When the procedure of Example 4 was repeated using, however, Preparation No. 3 having a different comonomer ra~io (90:10), it was found that the etch rate of the resi~t was increased to 1100 A/min. This less desirable result is a further indication of the preference for polymers containing 30 at least 2j mole percent of the hydroxyethyl comonomer.
Exam les 5-7 Additional Pol mer ExamDles P Y . _ The procedure of Example 1 was repeated, but using instead the polymers listed in Table III.

l :l B1192 T~ble IlI
____._ Sen~itivity Example Polymer Mw (C~ulomb~cm2) poly[4-but-1-enyl 64,100 7 X 10 8 methylacrylate-co-(2-hydroxyethyl meth-acrylate)](75 25) 7 6 poly[allyl methacrylate- 43,094 4.5 X 10-co-(2-hydroxypropylmeth-acrylamide)]
7 poly[3-norbornenyl meth- 64,078 8.6 X 10-8 acrylate-co-(2-hydroxy-ethyl methacrylate)]
(75:25) 1~ Unlike most of the previou~ example~, this was tested using a 20 keY electron beam. As is well known, 8 beam of half that energy increases the sensitivity value, and it i~
estimated such increased value would be well within the 2 X 10-7 coulomb/cm~ criterion. 0 Comparative Exam~le The procedure of Example 1 was repeated, except that the polymer tested was poly[methyl methacrylate-co-(2-hydroxyethyl methacrylate)](75 25) having 2 weight-aver~ge molecular weight of 34,900. No 6ensitivity was ascert~inable 2~ even at dosages of up to 2 X 10 6 coulombs/cm2, using 10 keV energy source. This experiment demonstrate~ the importance of the presence of ~he allyl group. Furthermore, it suggests that the failure of ~-hydroxyethyl methacrylate'~
performance reported in the afores~id British Patent Specification 1,407,312 i5 not due to the methyl group ~s reported, but rather i8 due to the ~e therewith of the methyl methacrylate comonomer.
The invention has been described in detail with par~
ticular reference to prefer~ed embodiments thereof, but it will be understood that variations and modifications can be effected within the spirit and scope of the invention.

Claims

What is Claimed is:
l. A polymer having a negative-working electron sensitivity of at least 2 X 10-7 coulomb/cm2 when,ex-posed to a 10 key electron beam, said polymer having recurring units with the structure wherein R and R1 are each independently hydrogen or methyl, or n is 1, 2, or 3;
R3 is alkylene of from l to 3 carbon atoms;
T is -O- or -NH-; and x and y are mole percents such that 50 < x < 95 < y < 50.
2. A polymer having 2 negative-working electron sensitivity of at least 2 X 10-7 coulombs/cm2 when ex-posed to a 10 key electron beam, said polymer having recurring units with the struc-ture wherein R and R1 are each independently hydrogen or methyl, R3 and R4 are each independently alkylene of from 1 to 3 carbon atoms;
T is -O- or -NH-; and x and y are mole percents such that 50 < x < 95 < y < 50.
3. Polyl(allyl methacrylate-co-(2-hydroxyethyl meth-acrylate) x:(100-x) wherein x is between about 50 and about 95 mole percent.
4. Poly[4-but-1-enyl methacrylate-co-(2-hydroxy-ethyl methacrylate)]x:(l00-x) wherein x is between about 50 and about 95 mole percent.
5. Poly(allyl methacrylate-co-2-hydroxypropylmeth-acrylamide)x:(l00-x) wherein x is between about 50 and about 95 mole percent.
; 6. Poly 3-norbornenyl methacrylate co-(2-hydroxy-ethyl methacrylate)x:(100-x) wherein x is between about 50 and about 95 mole percent.
7. A polymer as defined in claim 1 or 2, and further including a substrate bearing said polymer.
8. Poly[allyl methacrylate-co-(2-hydroxyethyl meth-acrylate)]x:(100-x) wherein x is between about 70 and about 75 mole percent.
9. Poly[but-l-enyl methacrylate co-(2-hydroxyethyl methacrylate)]x:(100-x) wherein x is between about 70 and about 75 mole percent.
10. Poly(allyl methacrylate-co-2-hydroxypropylmeth-acrylamide)x:(l00-x) wherein x is between about 70 and about 75 mole percent.
11. Poly[3-norbornenyl methacrylate-co-(2-hydroxy-ethyl methacrylate)x:(l00-x) wherein x is between about 70 and about 75 mole percent.
12. A method of imagewise hardening, on a sub-strate, a layer of a resist comprising a polymer as defined in claim 1 or 2, said method comprising the steps of a) imagewise exposing said layer to electron beam radiation of an energy no greater than about 10 key; and b) developing the layer by washing it with a sol-vent for the unexposed polymer .