Ⅱ-6

*-**
Structural analysis of photoresist
at boundary area in resist pattern
It is very important for further miniaturization of semiconductor devices to investigate correlation
between chemical structure of resist and Line Width Roughness (LWR). In this study, a novel
sampling technique and Pyrolysis-GC/MS combined with micro-GPC enable usto analyze
chemical structures of resist pattern in detail.

Approach for LWR analysis

Optical intensity in L/S pattern (simulation) Problems
High
①How to collect the resist at boundary area?
②How to analyze small amount of the collected
Boundary area sample?
Low

・The optical intensity was dramatically changed Novel method for the analysis of resist pattern
at boundary area.
Solution①：Establishment of sampling method
・The solvent in which resist-components moderately
The resist pattern at boundary area was analyzed. dissolve is selected.
Samples ・The boundary area (surface) of resist pattern is
collected by soaking in organic solvent for a short time.
Lithographic performance
Polymer PAG Illumination
（70nmL/40nmS）
Solution②：Application of micro-GPC
・GPC Fractions are dropped on sample plate or cup directly.
Large F F
Annular LWR: 7.0 nm
Ecd: 15.5 mJ/cm2
Accordingly it is easy to be applied to IR, Pyrolysis-GC/MS
group
F F
SO3- S (Py-GC/MS) and MALDI-MS measurements.
Dipole LWR: 5.0 nm ・Injection volume: tens of micrograms.
Ecd: 13.5 mJ/cm2

Results of analysis for resist pattern

Comparison between core and surface (boundary area) Comparison between illumination conditions (surface)
Photolysate of PAG
Surface Core
Relative intensity of protecting group （%）

Soaking in
organic solvent Polymer 50

Si Wafer blank Dipole

Py-GC/MS 40
Resist pattern after exposure and washing Resist pattern after soaking Annular
Annular
Relative intensity of protecting group （%）

Photolysis product 55 Dipole 30

from PAG Protecting group：
6 8 10 12 (min)
14
45 Annular＜Dipole
Surface GPC chromatogram 20
From polymer Py-GC/MS 6 8 10 12 14
35 Peak Intensity：Annular＞Dipole
Core GPC Retention time (min)
blank
25
＜Features of Annular＞ Simulation
Core 15 At surface of resist, polymer
Surface has more protecting groups. From GPC measurement
6 8 10 12 14 (min.) 5 More polymer were dissolved.
GPC chromatogram 6 8 10 12 14 ⇒ The boundary area was wide.
GPC Retention time (min.)
From Py-GC/MS measurement Annular
Information for boundary area was obtained. Deprotection reaction more proceeded.
⇒ This area was illuminated halfway.
Reaction mechanism of resist
The optical contrast was low.
Large
group
F F
h Large
F F
S These results were consistent with Dipole
SO3 group ＋
F F S SO3H simulation result.
F F
Acid Product of photolysis Conclusion
PAG A novel method for the direct analysis of the boundary
area in resist pattern was developed.
O O O O O O O O
O O O O O
H
O O
H
O The difference of the optical contrast at boundary area
Protecting
group
Lactone
Protecting
group
Lactone Lactone Lactone was related to the actual chemical structures.
Resist polymer De-protection: lowering of solubility to organic solvent “Joint study with JSR Corp.”
2014年6月TRCポスターセッション2014 No. Ⅱ-6
P01181有機分析化学第１研究室20140513
STC：開(20140515)