Electron beam hardening of photoresist

w. R. Livesay, A. L. Rubiales, M. Ross, S. Woods, S. Campbell

Electron Vision Corporation, San Diego, California 92126

ABSTRACT
Electron beam hardening is investigated and compared with conventional thermal hardening on a diazoquinone
novolak (DQN) photoresist. The electron beam hardening is accomplished without significant heating of the resist
thereby eliminating resist flow or melting. The electron beam cured polymer is fully cross-linked throughout its
entire thickness (full matrix cure). Thermal stability of the resist versus electron beam dose is examined. The
results of varying amounts of electron beam dose show that the shrinkage of the photoresist can be reduced almost to
zero by sufficient curing. The elimination of shrinkage of the resist also greatly reduces the amount of stress in the
cured film. After this electron beam cure, no resist stress or shrinkage is experienced even when the resist is
subjected to thermal bakes in excess of 200C. In fact, thennal stability of better than 400C has been
demonstrated. The resist shrinkage is eliminated due to the resist being fully cross-linked well below its glass
transition temperature. These fully cross-linked resists exhibit superior performance in plasma processing and yet
remain strippable by conventional plasma ashing processes.

1. BACKGROUND
1.1 Thermal hardening
Hardening of photoresist via post baking after image development is performed to strengthen the resist film so
that it can withstand the rigors ofplasma etching and other harsh processes.' Conventional post-baking or hardening
of photoresist is typically a trade-off between resist stabilization and melting. Melting temperature is proportional
to the molecular weight or degree of cross-linking in the film. As the molecular weight is increased, the glass
transition temperature is raised. In DQN resists, melting occurs above 135C. The postbake heating can cause the
exterior of the patterned resist to form an oxidized crust Nitrogen gas evolved from the DQ decomposition is
trapped by the crust inducing stress into the film which may cause edge lifting later in wet etching.2 DQN resists
baked in air at temperatures above 170C become insoluble due to oxidation and cross-linking. Below this
temperature the resist can be stripped in organic solvents. Although the chemical cross-linking of DQN competes
with physical melting, long slow bakes (120C for 16-24 hours) in air can achieve a high degree of thermal stability
(cross-linking) while minimizing resist flow (oxidation and ketene reactions harden the resist). However,
throughput considerations dictate raising the resist temperature rapidly (to increase the rate of cross-linking) while
keeping it below the glass transition temperature (Tg) to avoid melting the lithographic features.

1.2 Ultraviolet hardening

Radiation (UV) hardening has been a popular technique to harden the outer shell of the resist thereby allowing
higher posthake temperatures to be attained without destroying the pattern image. However, novolak resins absorb
strongly in the ultraviolet, preventing films thicker than 250-300 nanometers to be hardened. Combining UV
radiation with hot plate (ramped) baking of the resist allows for a more time efficient process.3'4 A fast cure can be
obtained by encapsulating the bulk of the resist (which is being cured by the hot plate) with the UV cured surface
film. The bulk resist temperature (ramped from a lower temperature) is kept below the glass transition temperature
of the surface cured film. The process requires careful balancing of the skin cure (it must be uniform) so that it will
hold the bulk of the resist from flowing while the hot plate is ramped close to the Tg of the resist. The surface of
the resist obtains a harder cure (tJV +bake) than the bulk (thermal cure only). The harder cured surface layer while
holding together lithography features, may also encapsulate some of the volatiles and solvents. When the resist is
later subjected to temperatures which exceed the postbake temperature (i.e. plasma etching or ion implantation)
solvents evolved can wrinkle or crack the brittle surface layer of the resist (reticulation).

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o-194-o827-1/93/$6.OO

2.0 ELECTRON BEAM HARDENING

The advent of sub-micron and higher aspect ratios in lithography features has intensified the need to eliminate
melting or any flow of the resist in the hardening process as well as eliminating reticulation in subsequent processes.
Sevemi years ago an electron beam exposure tool was proposed for curing and hardening photoresist.5'6 This new
type of hardening tool has shown promise in eliminating some of these process problems. In this paper we look at
some of the aspects of electron beam curing and the characteristics of an electron beam stabilized DQN photoresist

2.1 Electron beam interaction with polymers

An electron impinging on a polymer resist can have two kinds of encounters, nuclear and electronic. Nuclear
collisions (Rutherford scattering) are elastic and merely change the direction of the electron. Electronic collisions are
inelastic and slow down the primary electron trsnsfemng its energy into excitation energy and kinetic energy of
secondary electrons. As the electrons slow down from collisions with the polymer molecules they excite and impart
energy to the molecules and ionize them. Secondary electrons are emitted with relatively slow speeds and produce
many more ions along the track of the primary electron beam. The impinging electrons have a very large number
of inelastic collisions with electrons of different energy states before they are slowed down enough to be absorbed.
Within a picosecond (1012 ) after ionization, molecular rearrangement takes place in the ions and excited
molecules, accompanied by thermal deactivation or the disassociation of valence bonds.8 The radicals, created by
these broken bonds, form new bonds and reattach themselves to neighboring polymer chains which also have broken
bonds in their side groups. These additional bonds strengthen the molecules against backbone damage and tie smaller
molecules together into larger clumps of higher effective molecular weight. Cross-linking continues for higher
doses and is accompanied by the formation of gel and ultimately by the insolubalization of the entire coating.
This extensive cross-linked network of molecules extending throughout the entire coating makes the polymer
stable to heat such that it cannot be made to flow or melt. A fully cross-linked polymer is insoluble in all solvents.
The resulting polymer coating can still be removed by oxygen plasma etching even though it cannot be removed by
chemical stripping methods. Depending on the material, the electron beam curing can improve the plasma etch
resistance of the coating but only to varying degrees. The plasma etch resistance of a polymer is mostly a function
of it's basic structure (backbone) and not the degree of cross-linking. However, electron beam curing can
significantly improve the plasma etch stability of the polymer in eliminating reticulation and melting caused by
heating by the plasma.
2.2 Efficiency of cure

Electron beam curing is very energy efficient compared to other processes. Rather than heating entire ovens or
hot plates most of the beam energy goes into curing the resist. High efficiency is achieved by assuring that most of
the beam energy is absorbed in the material to be cured and not in the underlying substrate.6 Thinner resists require
less dose than thicker resists to achieve the same hardening properties. By adjusting the energy of the beam such
that the range of the incident electrons is nearly equal to the resist thickness provides for an efficient means of
maximizing throughput while providing a nearly uniform cure throughout the full thickness of the resist.
2.3 Electron beam exposure system
The electron beam exposure tool used for these experiments is specifically designed for electron beam curing of
photoresists and interlayer dielectrics.9 The electron optical column in this system produces a large collimated
electron beam which totally covers the sample being processed up to 200 mm in diameter. This electron beam tool,
further described elsewhere,'0 utilizes a cold cathode which is impervious to the gaseous products evolved from the
resist and allows it to operate in a soft vacuum environment (1-5 Pa).

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2.4 Radiation and charging effects

In conventional electron beam exposure systems (SEMs, etc. ) surface charging by the eleciron beam is a
problem for insulating samples. However, by operating in a soft vacuum environment electhcal charging of the
sample does not occur. The induced charge at the surface of the sample is neutralized by positive ions generated by
the electron beamS This allows exposure of insulating samples without the requirement of a conductive coating.
Also the electrical charge injected into the interior of an insulating coating is diminished or drained by electron beam
induced conductivity (EBIC) created by the curing beam. This allows the charge to be drained by positive ions on
the surface of the sample. The effect on circuit devices (oxide gates, etc.) by the high dose of electron beam curing
(typically lOx to 20x higher than E-beam direct write exposure doses) has not been determined. Researchers have
reported both beneficial and deleterious effects of e-beam exposure on semiconductor devices."2'13 E-beam curing
is being used today in areas where it is followed by an annealing step in a subsequent process or on substrates with
no active devices (i.e. thin film heads, multichip modules, etc.), or where the active device is protected by another
layer. No exhaustive study has been done to determine the effect on unprotected oxides.

3.0 PROPERTIES OF ELECTRON BEAM CURED PHOTORESISTS - EXPERIMENTS

3.1 Thermal stability
A diazonapthoquinone novolak positive photoresist, Nova 2071 (40% solids)'4 was tested for thermal stability
after electron beam curing. Similar tests have been run on other DQN resists. The results presented here on Nova
2017 are representative of the effect electron beam curing has on DQN resists in general. Nova 2071 (40%) is used
for single spin-on application of 3-10 un thick resist layers. Thicker resists, in general, are more prone to in-plane
pattern distortion via melting-than thinner resists. Melting or pattern distortion can occur for temperatures above
125C with this resist using conventional thermal hardening. For these electron beam curing tests, wafers were
coated, prebaked, patterned, and developed (see Tables 1-5). They were than cured via electron beam at various
dosages. After electron beam curing the samples were baked at various temperatures, cleaved and their edge profiles
photographed (SEM). Figure 1 through Figure 5 show the thermal stability imparted by the electron beam curing
process. In Figure 1, a wafer (control) without an electron beam cure (dose=O) is subjected to a series of postcure
bakes. The resist sidewall profile for a 5 pin feature is shown before baking (Figure la). In Figure lb the same
feature is shown after a 130C bake for 60 seconds (this temperature is 5C higher than the recommended postbake
temperature for this resist). Note the slight bulging of the sidewall indicating the onset of melting of this resist. At
180C (Fig.lc) and higher temperatures (Fig. id and Fig. le) the resist bulges then flows. Figure 2 shows the effect
of the same postcure bakes but on a sample that has received an electron beam dose of 500 pC/cm2. As shown by
Figure 2b through Figure 2e this relatively low dose has stabilized the resist except for the two hour 225C
convection oven bake. With this longer bake a slight bulge is seen at the top of the feature with the sidewall
showing no deformation. With higher cures (Figure 3a-e: dose =1000 Uiii2 and Figure 4a-e: dose =2000
j.unC/cm2) there is no detectable resist distortion or flow at all bake temperatures. Note how the standing wave
pattern created by the optical lithography step is preserved in all of the electron beam cured cases. Further curing
even at a dose 20 times that required to thermally stabilize the resist, shows no ill effects in the resist profiles
(Figure 5a-e) . Thus, even on very heavy doses where the resist is cured to a hard plastic state, no change in resist
wall slopes or critical geometries is experienced.
Without deleterious effects caused by overcure, process windows can be widened, thereby enhancing process
repeatability and yield. Further, the uniformity of the exposure source (which is so critical in a UV/skin bake
process) is greatly relaxed. The degree of cross-linking reaches an asymptotic level such that any nonuniformity in
the curing beam (across the wafer) can be eliminated by simply increasing the dose.

3.2 Solubility vs. dose

When a DQN photoresist is irradiated with an electron beam at low dose, chain scissions predominate,
increasing the solubility of the resist. As the dose is increased, cross-linking predominates making the resist

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insoluble. Exposures were made on Nova 2071 diazonapthoquinone novolak (DQNIn)resist (- 4 jim thick) coated
on bare silicon wafers. The solubility of the resist as a function of exposure dose was evaluated by immersing the
exposed samples in undiluted developer (Morton DE-3 O.5N) and monitoring the development rate. Development
rate was determined by measuring resist thickness remaining over a range of development times. Figure 6 shows the
solubility vs electron beam dose. In a separate set of tests, the resistance to organic solvents was evaluated. For
more aggressive strippers (i.e. acetone based) dose levels of 2000-4000 pC/cm2 or greater are required to make the
resist insoluable. At these and greater dose levels the resist is inert in wet solvents and hot strippers. It is surmised,
at these higher dose levels the cross-linked matrix of polymer chains is so dense that openings in the film are too
sniall for solvent molecules to penetrate. The amount of dose required for a given process is dependent on the resist
characteristics desired and the thickness of the resist. For example a process may require that the resist hold up to an
etching step or a plating bath and then be removed in a wet stripper (as opposed to plasma ashing). In Figure 7 the
thermal stability and solubility are plotted vs dose. A hypothetical process window established by a minimum
solubility requirement (dose '8OO .tCIcm2) and a minimum resist thermal stability of 1800 C (dose 6OO j.Lcicm2)
is shown by the vertical lines in Figure 7. If the entire resist layer is hardened uniformly than it is possible to
select a dose within this process window that either optimizes solubility or optimizes thermal stability, In a
UV/skin bake process there are large differences in the degress of hardening throughout the resist layer. In dense
lithographic areas there is a greater ratio of resist surface to bulk. In a UV skin/bake, the surface (and areas close to
the surface) are cured to a higher level than the bulk of the resist. Therefore, the denser lithographic areas have a
harder cure than those areas with fewer features. if the difference in resist hardness is larger than the process window
then a portion of the resist may have the thermal stability but not be removable via a wet solvenL Another portion
of the resist may be removable via wet stripper but not hold up to the thermal process. Electron Beam curing can
obtain a uniform cure throughout the entire resist layer. Therefore with E-beam curing one may work at either
extreme of the process window to optimize for either ease of removal or thermal stability. (i.e. if the resist is
uniformly cured at a lower level of cross-linking it is much easier to strip in subsequent operations).
3.3 Resist shrinkage and stress
Shrinkage occurs during resist post baking due to the evolution of diazoquinone and solvents not evolved in the
prebake . Since the resist layer is constrained by the substrate in two dimensions, shrinkage of the film only occurs
in the vertical dimension. A 15% - 18% resist thickness loss can occur during baking due to the evolution of
solvents, diazoquinone, water, nitrogen, hydrogen etc. Baking of the resist also induces stresses in the films due to
the mismatch of thermal expansion between the resist and the substrate. Stress induced in thermal curing has been
found to be independent of the coating thickness and solution concentration.'5 Narrow molecular weight polymers
(usually required for high contrast development) without added plasticizers can become brittle and crack High bakes
may induce internal stresses in DQN resists to cause edge lifting in aqueous etchants. The edge lifting, due to
internal stresses, can cause severe undercutting of small resist islands.
Resist shrinkage is greatly reduced in electron beam curing. Film thickness measurements made before and after
E-beam curing indicate little or no shrinkage of the resist. Measurements on Nova 2071 electron beam cured resists
showed zero to less than 2% resist thickness loss (within experimental error) as compared to 15% - 18% resist
thickness loss using thermal curing. Induced stress in electron beam cured films have shown similar improvements.
Measurements made after electron beam curing and during subsequent baking have also shown little or no stress in
the cured films. To evaluate resist shrinkage after E-beam cure, DQN resist coated samples were exposed at varying
dose and subsequently baked at high temperature. Figure 8 shows the amount of shrinkage of a DQN based resist
(2.3 pin thick original thickness) as a function of dose when postcured baked at 225C. Note that dose levels of
2000-4000 jiC/cm2 are required to minimize shrinkage. It is believed that the shrinkage which occurs below
exposure doses of 4000 iC/cm2 is due to the expulsion of solvents or other volatiles not yet evolved (or not broken
down and cross-linked into an unreactive component of the film). For doses below 4000 j.tCIcm2 components in
the solvents may react with some etchant gases (in certain processes) to create surface films which would necessitate
an additional descum process. Therefore, for resist films that will see very harsh process environments or are required
to become permanent structures and remain inert, an electron beam curing dose of at least 4000 ixC/cm2 appears
necessary. With little or no resist shrinkage using electron beam curing, the possibility exists for eliminating some
steps required to planarize resist that has shrunk unevenly over circuit features of differing elevations.

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4.0 CONCLUSIONS
Electron Beam cunng/har&ing ofDQN photoresists was investigated and compared with conventional thennal
curing. Electron Beam hardening of photoresist can attain distortionless stabilization of DQN resists by utilizing
full matrix cross-linking of the resist. The thermal glass transition temperature can be raised to over 400C without
resorting to long slow bakes. Thermal stability can be improved which preserves lithographic features. Solubiity
of the resist is dose dependent which means etch resistance can be determined by needs of downstream processes.
Little or no shrinkage is experienced in the cured resist layer providing a means of improving planarization on wafers
with large topographical differences. The elimination of shrinkage also reduces the stress in the film even for
subsequent thermal processes. In many applications E-Beam curing of resist provides improved performance over
traditional curing methods.

5.0 ACKNOWLEDGEMENTS
The authors gratefully acknowledge the contributions of the following individuals whose support made this
paper possible: Tom Eichenberg and Ken Bell of Morton International for helpful discussions and the thennal
stability micrographs and processing, Tyler Curtis of AMCC for thin film measurements.

6.0 REFERENCES
1. W. Moreau, Semiconductor Lithography, 545,Plenum (1988)
2. H. Vanazawa, N. Hasegawa and K. Donta, J Appl. Polym. Sci. 30,547(1985)
3. J. C. Matthews, J. Wilmott, SPifi Proc. 470, 194 (1984)
4. U.S. Patent 4,548,688 (1985) Fusion Semiconductor Systems
5. P. Burggraaf, Semiconductor International, P.89 April 1987

6. W. Livesay, Radtech '90, Pg 195. 1990

7. A. Chapiro, Radiation Chemistry of Polymeric Systems, 42, Wiley (1962)
8. F. Bilhneyer, Texthook of Polymer Science, P.372, Wiley (1971)
9. ElectronCure 3Oxfl&200A manufactured by Electron Vision Corporation.
10. To be published - Symposium on Electron Ion and Laser beams - June 93
11. J. Dunn, B. J. Gross, C. G. Sodmi - IEEE Trans. on Electron Devices, Vol. 39 No. 3 P.677, March 1992
12. J. M. Aitken, C. Y. Ting, IEDM, December 1981
13. M. Peckerar, R. Fulton, P. Blaise, D. Brown, R. Whitlock, J.Vac. Sci. Technol. 16(6) Nov.IDec. 1979
14. K. Bell, N. Acuna, S. Dixit, R. Lazuarus, G. Talor, SPIE Vol. 1672, 597 (1992)
15. S. Croll, J. Appi. Polym. Sci. 23, 847 (1979).

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Table 1
Resist:

Morton-NOVA 2071 (40%)

Film Thickness:

3.7 microns

CD:

5 microns

Softbake:

85C/i 10 seconds

120C/hO seconds

Exposure:
Develop:

360
Ultratech 1000 (NA=0.315)

Immersion (1 Minute)
DE-4, 23C

Resist Hardening: None - Control Wafer

Figure lb. 130C/60 Seconds

Figure 1 c. 180 C/60 Seconds

Figure id. 230C160 Seconds

Figure 1 Resist thermal stability zero

Figure le. 225C/2 Hours Convection

dose

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Vol. 1925 1431

Table 2
Resist:

Morton-NOVA 2071 (40%)

Film Thickness:

3.7 microns

CD:

5 microns

Softbake:

85C/i 10 seconds
120C/i 10 seconds

Exposure:
Develop:

Resist Hardening:

360 mi/cm2
Ultratech 1000 (NA=0.315)

Immersion (1 Minute)
DE-4,23C

500 pC/cm2 @ 15 keV

ElectronCure 30X-200A
Figure 2a. No bake

Figure 2b. i30C/60 Seconds

Figure 2c. 180C/60 Seconds

Figure 2d. 230C/60 Seconds

Figure 2e 225C/2 Hours Convection

Figure 2 Resist thermal stability after 500 pC/cm2 dose

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Table 3
Resist:

Morton-NOVA 2071 (40%)

Film Thickness:

3.7 microns

CD:

5 microns

Softbake:

85C/i 10 seconds
120C/i 10 seconds

Exposure:

360 mJ/cm2
Ultratech 1000 (NA=0.315)

Develop:

Immersion (1 Minute)
DE-4,23C

Resist Hardening: 1,000 .tC/cm2 @ 15 keY

ElectronCure 30X-200A

Figure 3b. 130C/60 Seconds

Figure 3d. 230C/60 Seconds

Figure 3a. No bake

Figure 3c. 180C/60 Seconds

Figure 3e. 225C/2 Hours Convection

Figure 3 Resist thermal stability after 1,000 RC/cm2 dose

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Table 4

iIpI7

Resist:

Morton-NOVA 2071 (40%)

Film Thickness:

3.7 microns

CD:

5 microns

Softbake:

85C/i 10 seconds
120C/i 10 seconds

Exposure:

360 ipJ/cm2
Ultratech 1000 (NA=0.315)

Develop:

Immersion (1 Minute)
DE-4,23C

Resist Hardening:

2,000 .tC/cm2 @ 15 keV

ElectronCure 30X&200A

5KV X15888

h'i

Figure 4b. 130C/60 Seconds

Figure 4d. 230C/60 Seconds

Figure 4a. No bake

1D19
Figure 4c. 180C/60 Seconds

Figure 4e. 225C/2 Hours Convection

Figure 4 Resist thermal stability after 2,000 iC/cm2 dose

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Table 5
Resist:

Morton-NOVA 2071 (40%)

Film Thickness:

3.7 microns

CD:

5 microns

Softbake:

85C/lb seconds
120C/lb seconds

Exposure:

360 mi/cm2
Ultratech 1000 (NA=0.315)

Develop:

Immersion (1 Minute)
DE-4,23C

Resist Hardening:

20,000 p.C/cm2 @ 15 keV

ElectronCure 30X&200A

Figure 5b. 130C/60 Seconds

Figure 5a. No bake

Figure 5c. 180C/60 Seconds

Figure Sd. 230C/60 Seconds

Figure Se. 225C/2 Hours Convection

Figure 5 Resist thermal stability after 20,000 p.C/cm2 dose

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C)

Resist:

Nova 2071

Develop: DE-3 0.5N

Exposure: ElectronCure 30 System

.0

(I)

100 200 300 400 500 600 700

Dose (RC/cm2)

Figure 6. Solubility vs. dose

i3O0
o 250

. 200
150

C,)

50
0 500 1000150020002500300035004000
Dose (pC/cm2)
Figure 7. Solubility & Tg vs. dose
1

16

ci)

0)
12
E 10
C,)

0)4.
C,)

2
0

500 100015002000250030003500 4000

Dose (p.C/cm2)

Figure 8. Resist shrinkage vs. dose for postcure 225C bake

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