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1
NO.1
Improved Resolution of Thick Film Resist
(Effect of Development Technique)
Yoshihisa Sensu, Atsushi Sekiguchi and Yasuhiro Miyake
Litho Tech Japan Corporation
2-6-6 Namiki, Kawaguchi, Saitama, 332-0034, Japan
2
NO.2
(DNQ)Si 24
Q4000
N2
MEMS(Micro Electro Mechanical Syatems)TAB(Tape Bonding)
COG(Chip On Glass)CSP(Chip Scale Package)
[1]IC
[2]
[3]
Q4000[4]
RDA[5]
SOLID-C[6]
N2
3
NO.3
2.
2.1
(DNQ)
N2
N2
N2N2
N2
N2
2.2
(1)
Q4000 Q4000
[4]
RDA[5]
SOLID-C[6]
Litho Spin Cup[4]
23.731.7
() Si
24m
1107 15
30 [3]
(2)
Dipping Development ( DD )
(a)
Step Puddle Development ( SP )
(b)
100rpm 5 295 3
Vibration Development ( VD )
4
NO.4
(c)
50Hz 50m
Reverse Development ( RD )
(d)
(3)
Q4000 Quintel
TMAH
()23 15
10m 3.5(LineSpace11)i
10m 11 (Eop)
(4)
RDA[5] 950nm
Q4000
TMAH
SOLID-C[6]
[7] NA0.1
0.999 11
10m 4.0(LineSpace11)
10m 11 (Eop)
(5)
13 35
N2 N2
[8]
(6)
23
3.
3.1
SP 3.5mVD 4.0mDD 4.0m
RD 4.0mSP 4
5
NO.5
SP VD DD RD
RD
SP VD DD
RD
3.2
[9](
: tan)(Eth)
tanSP 3.4VD 2.9DD 2.3
RD 1.3 15
SP 14.6VD 8.7DD 8.0 RD 3.0 tan
15 (Eth)
SP 361.5mJ/cm2VD 377.4mJ/cm2DD
455.7mJ/cm2 RD 510.4mJ/cm2 SP
4.
4.1
SP VD DD RD
SP VD
DD RD SP
R(E) R E
SP VD DD
RD
4.2
350mJ/cm2
700mJ/cm2
(Activation energy) Frequency factor Kd
[10]
2ln
RTE
dTkd d = (1)
6
NO.6
E (kcal/mol)T (K)Kd(S-1)
350mJ/cm2 SP 29.97kcal/molVD 11.25kcal/mol
DD 4.41kcal/mol RD 1.14kcal/mol SP VD
DD RD
N2RD DD
) N2
N2 RD N2
SP VD
N2 (Eth)
350mJ/cm2 N2 SP VD
DD RD
() N2
DD RD SP
RD
() N2
N2 700mJ/cm2
DD VD
N2
N2 N2
N2
N2 N2
[8]
Z Z0 e(-E/RT)
23 1ml N2
1923
10554.2100029608204.0
102023.6=
==RTNn (2)
N Avogadro R (l atm/deg mol)T K
1sec N2 Z0
5.022
0 2
=MRTnZ (3)
n 1ml N2 N2(cm)M N2
7
NO.7
Z
RTE
eZZ
= 0 (4)
E (kcal/mol)
N2
350mJ/cm2 SP 4.60106molecule/secVD 3.061020molecule/sec
DD 3.441025molecule/sec RD 8.941027molecule/sec
N2
N2
350mJ/cm2 700J/cm2
350mJ/cm2 N2
4.3
SP VD SP SP VD
2.6mg/ml 5.5mg/ml
SP N2
5.
SP VD DD RD
N2N2
N2 N2
(SP VD
)(DD RD N2
N2
8
NO.8
N2
Q4000
Quintel Jeffrey Lane
SIGMA-C Dr. Christian K. Kalis
[1] R. Arai, "Exposure machine for the magnetic head, " Electric Parts and Materials,
pp. 84-89, Feb. 2000. [2] Y. Shibayama, and M. Saito, " Influence of Water on Photochemical Reaction of
Positive-Type Photoresist, " J. Appl. Phys. , vol.29, pp. 2152-2155, Oct. 1990. [3] , , , " , "
(C), vol. J85-C, no. 4, pp. 260-268, Apr. 2002. [4] Y. Sensu, A. Sekiguchi, and Y. Miyake, : Improved Resolution of Thick Film
Resist (Effect of Development Technique), Proc. SPIE, vol. 4690, pp. 861-882, Mar. 2002.
[5] A. Sekiguchi, C. A. Mack, Y. Minami, and T. Matsuzawa, " Resist Metrology for Lithography Simulation, Part 2 : Development Parameter Measurements, " Proc. SPIE, vol. 2725, p. 49, Mar. 1996.
[6] Erddmann A, Henderson C. L, Willson C. G, Henke W, " Influence of optical nonlinearities of photoresists on the photolithographic process : Applications, " Proc. SPIE, vol. 3048, pp. 114-124, Mar. 1997.
[7] Y. minami, A. Sekiguchi, " Deforcus Simulation Using Observed Dissolution Rate in Photolithography, " Electronics and Communications in Japan, Part 2, vol. 76, No. 11, pp. 106-115, Nov. 1993.
[8] , , " , " pp. 37-39, , , 1993.
[9] T. Kokubo, " History of Research and Development for Positive Photoresist, " Fuji Film Research and Development, No. 34, pp. 21-31, 1989.
[10] , , , " , " pp. 278-307, , , 1967.
9
(tan)(Eth)
Table 1 Development contrast (tan), values, and Eth for the different development
methods.
Development Method tan value Eth(mJ/cm2) Eop(mJ/cm2)
SP Method 3.4 14.6 361.5 540.0
VR Method 2.9 8.7 377.4 550.0
DD Method 2.3 8.0 455.7 580.0
RD Method 1.3 3.0 510.4 590.0
(a)350mJ/cm2 (b)700mJ/cm2
Table 2 Development reaction rate constants for exposure doses : (a) 350 mJ/cm2 and (b)700
mJ/cm2
(a)Exposure dose : 350 mJ/cm2
Dipping Development Method (DD Method) (S-1)
Development Temperature (1/T) Exposure dose: 350mJ/cm2
3.4810-3 6.8010-4
3.4310-3 7.3010-4
3.3810-3 6.6010-4
3.3510-3 7.0010-4
3.2810-3 6.7010-4
Vibration Development Method (VD Method) (S-1)
Development Temperature (1/T) Exposure dose: 350mJ/cm2
3.4810-3 8.3010-4
3.4310-3 9.5010-4
3.3810-3 11.5010-4
3.3510-3 13.6010-4
3.3010-3 23.0010-4
Step Puddle Development Method (SP Method) (S-1)
Development Temperature (1/T) Exposure dose: 350mJ/cm2
3.4910-3 5.4010-4
3.4110-3 8.2010-4
3.3810-3 10.2010-4
3.3710-3 12.5010-4
3.3510-3 15.7010-4
10
Reverse Development Method (RD Method) (S-1)
Development Temperature (1/T) Exposure dose: 350mJ/cm2
3.4610-3 1.6410-3
3.4110-3 1.7010-3
3.3810-3 1.7210-3
3.3410-3 1.8510-3
3.3210-3 1.9210-3
(b)Exposure dose : 700 mJ/cm2
Dipping Development Method (DD Method) (S-1)
Development Temperature (1/T) Exposure dose: 700mJ/cm2
3.4810-3 2.2710-3
3.4310-3 3.0110-3
3.3810-3 4.6610-3
3.3510-3 5.4310-3
3.2810-3 5.9810-3
Vibration Development Method (VD Method) (S-1)
Development Temperature (1/T) Exposure dose: 700mJ/cm2
3.4810-3 2.7910-3
3.4310-3 3.5410-3
3.3810-3 4.3810-3
3.3510-3 5.1910-3
3.3010-3 10.7310-3
Step Puddle Development Method (SP Method) (S-1)
Development Temperature (1/T) Exposure dose: 700mJ/cm2
3.4910-3 2.9010-3
3.4110-3 4.3610-3
3.3810-3 7.6010-3
3.3710-3 8.8010-3
3.3510-3 10.0010-3
Reverse Development Method (RD Method) (S-1)
Development Temperature (1/T) Exposure dose: 700mJ/cm2
3.4610-3 3.1110-3
3.4110-3 3.3210-3
3.3810-3 3.5310-3
3.3410-3 3.9410-3
3.3210-3 4.5610-3
11
N2
Table 3 Number of molecular collisions between the N2 deposition layer on the resist surface
and the N2 molecules released from the interior of the resist film.
(molecule / sec)
Development Method Exposure dose: 350 mJ/cm2 700 mJ/cm2
SP Method 4.60106 1.97102
VR Method 3.061020 6.501017
DD Method 3.441025 9.711018
RD Method 8.941027 6.421021
12
(DNQ) Fig. 1 Photochemical reaction scheme involving diazonaphthoquinone (DNQ) novolak-based
positive resist.
+ N2
13
Exposure system: Mask Aligner Q4000 (Quintel Corporation)
Development system: Litho Spin Cup Resist development rate measurement system: RDA
Fig. 2 Configurations of exposure, development, and analysis systems.
14
Resist spin coating
Pre-BakeProximity type 110/minutes
Vacuum desiccators 60minutes
With water 15/30minutes
Exposure (Vacuum contact Exposure)
Development (Dipping, Step puddle, Vibration, Reverse)
Fig. 3 Sample preparation process.
15
(a) Dipping Development Method (DD Method)
(b) Step Puddle Development Method (SP Method)
(c) Vibration Development Method (VD Method)
(d) Reverse Development Method (RD Method)
Fig. 4 Schematic diagrams of the development methods.
Resist
Si Wafer
Developer
Developer Cup
Developer Nozzle
Developer
Spin Chuck
Vibration
Vibration system
Resist
Si Wafer
Si Wafer
16
Line Width (m) Line:Space = 1:1
10 8 6 4 3.5
SP
Method
VD
Method
DD
Method
No resolution
RD
Method
No resolution
Illustration of resist pattern data
SP Method VD Method DD Method RD Method
The resist residues in the space area
Fig. 5 Resist pattern observation results for the defferent development methods.
Resist
residue
17
Development Method Development contrast (tan)
SP (Step Puddle) 3.4
VD (Vibration Development) 2.9
DD (Dipping Development) 2.3
RD (Reverse Development) 1.3
tan
Fig. 6 Comparison of discrimination curves and development contrast (tan) for the different
development methods.
0.01 0.1 1 10 100 1000 100001
10
100
1000
SP Method VD Method DD Method RD Method
Dev
elopm
ent
rate
(nm
/s)
Exposure dose (mJ/cm2)
18
Line:Space = 1:1
Line Width
(m) 10 8 6 5 4
SP Method
VD Method
No resolution
DD Method
No resolution
No resolution
RD Method
No resolution
No resolution
Development
Method
Eop (mJ/cm2 )
Line Width (m) 10 8 6 5 4
Sidewall Angle () 83.3 82.9 82.7 82.1 --------SP Method 439.7
Thickness Loss (%) 12.8 12.7 13.4 25.0 --------
Sidewall Angle () 82.9 82.6 81.4 -------- --------VD Method 466.0
Thickness Loss (%) 13.8 13.8 15.8 -------- --------
Sidewall Angle () 82.2 81.4 ------ -------- --------DD Method 503.2
Thickness Loss (%) 14.6 14.9 ------ -------- --------
Sidewall Angle () 82.3 81.4 ------ -------- --------RD Method 504.8
Thickness Loss (%) 13.6 13.8 ------ -------- --------
Fig. 7 Results of resist pattern simulations for the different development methods.
19
0.00325 0.00330 0.00335 0.00340 0.00345 0.003501E-4
1E-3
0.01
0.1
SP Method VP Method DD Method RD Method
Dev
elopm
ent
const
ant
(s-1)
Development temperature (1/T)
(a) Exposure doses : 350mJ/cm2
0.00325 0.00330 0.00335 0.00340 0.00345 0.003501E-3
0.01
0.1
SP Method VP Method DD Method RD Method
Dev
elopm
ent
const
ant
(s-1)
Development temperature (1/T)
(b) Exposure doses : 700mJ/cm2
(kcal / mol)
Development Method Exposure dose: (a) 350 mJ/cm2 (b) 700 mJ/cm2
SP Method 29.97 35.94
VR Method 11.25 14.87
DD Method 4.41 13.28
RD Method 1.14 9.46
(a) 350mJ/cm2 (b) 700mJ/cm2
Fig. 8 Arrhenius plots and activation energy for exposure doses : (a) 350mJ/cm2 and (b) 700mJ/cm2.
0.001
0.0001
0.001
0.01
0.1
0.01
0.1
20
(a) Model of closed-system development methods
(b) Model of open-system development methods
N2
Fig. 9 A model diagram describing the formation of an N2 deposition layer on the resist surface
during the development.
Exposure Area
Exposure Area
21
0 2 4 6 8 10 12 14
14
16
18
20
22
24
26
28
30
Dev
elopm
ent
rate
(nm
/s)
Concentration of dissolved resist material (mg/ml)
10
Fig.10 Relationship between the concentration of dissolved resist material and the development
rate.