Development of sub-10nm Patterns using Novel BCP · A block B block Mn fB Lo BCP1 21.6k 0.48 19.8nm...
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Jung-Keun Kim, Se Jin Ku, Hyung Ju Ryu, Jegwon Lee, Misook Lee, Nojin Park, Eunyoung Choi, Sung Soo Yoon* LG Chem, Corporate R&D, 188, Munji-ro, Yuseoung-gu, Daejeon, 305-738, Korea E-mail : [email protected] Development of sub-10nm Patterns using Novel BCP Development of sub-10nm Patterns using Novel BCP § The increasing demand for the development of novel BCPs suitable to DSA ü Line width less than 10nm ü Fast thermal annealing ü Perpendicular pattern formation without the need of a neutral layer ü Minimization of defects (< 0.01/cm 2 ) State of the Art Needs for BCP lithography Advantage: No surface modification Problem: Complicated pattern transfer Advantage: Simple pattern transfer Problem: Surface modification needed - Parallel cylinder - Perpendicular lamellar § Perpendicular lamellar morphology has advantage in a DSA process ü ~15nm line width pattern ü Thermal annealing is employed at over 200℃ ü A neutral layer is required to attain perpendicular pattern formation ü Number of defects (as of 2014): 24/cm 2 PS-b-PMMA : NL neutral layer top-coat layer neutral layer - Monomers are deliberately designed to afford the unique interactions developing sub-10nm morphologies - Low T g of novel BCPs allows structure formation exclusively by thermal annealing - Novel BCPs show intrinsic long range ordered structure due to high effective χ - Unique structural features of BCPs render perpendicular pattern formation on a substrate without any surface modification - Novel BCPs are applicable to graphoepitaxy DSA processes § LG novel BCPs generate perpendicular sub-10nm patterns without surface modification of silicon substrate LG Novel BCP : No neutral layer, No top-coat High χ BCP : NL+ top-coat spin coating brush and annealing removing excess brush spin coating BCP directed self-assembly PS-b-PMMA Process LG Flow : Additional processes to construct a neutral layer are necessary : No additional process is necessary for a DSA, presenting a much simpler process lithography spin coating BCP directed self-assembly silicon wafer § Novel BCPs facilitate the more simple process compared to the conventional chemoepitaxy crosslinking mat material lithography breakthrough etching trim etching stripping photoresist Hydrophobic Hydrophilic Hydrophilic water contact angle=85° : silicon wafer coated with Cu water contact angle=40° : bare silicon wafer water contact angle=15° : O 2 plasma-treated silicon wafer top surface SEM top surface SEM top surface SEM 50nm 50nm 50nm cross-section TEM cross-section TEM cross-section TEM § Pattern formation is unaffected by substrate surface conditions : Structures by novel BCPs show perpendicular lamellae orientation regardless of substrate surface properties § LG novel BCPs were synthesized successfully by conventional polymerization GPC A-B BCP A block 12 15 18 21 12 15 18 21 Mn L0 A block B block M n f B L o BCP1 21.6k 0.48 19.8nm BCP2 18.9K 0.43 17.5nm BCP3 15.4k 0.55 14.2nm BCP4 13.2k 0.56 11.6nm BCP5 17.8k 0.31 17.4nm Mn Ø The monomers A and B are designed to induce intermolecular interactions Ø GPC data verify the successful synthesis of BCPs with narrow PDIs Ø Series of BCPs with diverse M n and volume fractions were readily prepared Ø A linearly fitted M n to L o plot reveals a fully stretched BCP architecture Ø Perpendicular pattern formation without the aid of a neutral layer or top-coating Ø Pattern formation is unaffected by substrate surface condition Ø Realization of sub-10nm patterns of tunable size and morphology Ø Novel BCPs facilitate the more simple DSA process compared to the conventional chemical epitaxy ü Development of a new BCP capable of structure formation of broad pitch sizes and hole pattern top surface SEM top surface SEM top surface SEM FT FT FT 50nm top surface SEM top surface SEM 50nm cross-section TEM BCP1; L o =19.8nm BCP3; L o =14.2nm BCP4; L o =11.6nm § Realization of sub-10nm patterns of tunable size and morphology : Line patterns of around 5~10 nm line width are routinely generated within BCP thin films : Dot patterns of ~20nm pitch, 7.5nm diameter are routinely generated within BCP thin films BCP5; L o =~20nm BCP2; Lo=17.5nm Thickness: 40nm Trench: W=160nm /M=140nm /D=40nm BCP1; Lo=19.8nm Thickness : 25nm Thermal annealing : 160℃, 5min top surface SEM cross section SEM 100nm cross section TEM As-spun 5min 50nm TEM 50nm TEM - On bare substrates : perpendicular lamellar pattern - In trenched substrates : perpendicular lamellar pattern - Perpendicular lamellar pattern formation is originated from the top surface § Perpendicular pattern formation without the aid of a neutral layer or top-coating 50nm TEM 50nm TEM
Transcript of Development of sub-10nm Patterns using Novel BCP · A block B block Mn fB Lo BCP1 21.6k 0.48 19.8nm...
Jung-Keun Kim, Se Jin Ku, Hyung Ju Ryu, Jegwon Lee, Misook Lee, Nojin Park, Eunyoung Choi, Sung Soo Yoon*LG Chem, Corporate R&D, 188, Munji-ro, Yuseoung-gu, Daejeon, 305-738, Korea
E-mail : [email protected]
Development of sub-10nm Patterns using Novel BCPDevelopment of sub-10nm Patterns using Novel BCP
§ The increasing demand for the development of novel BCPs suitable to DSA
ü Line width less than 10nm
ü Fast thermal annealing
ü Perpendicular pattern formation without the need of a neutral layer
üMinimization of defects (< 0.01/cm2)
State of the Art Needs for BCP lithography
Advantage:No surface modification
Problem:Complicated pattern transfer
Advantage:Simple pattern transfer
Problem:Surface modification needed
- Parallel cylinder - Perpendicular lamellar
§ Perpendicular lamellar morphology has advantage in a DSA process
ü ~15nm line width pattern
ü Thermal annealing is employed at over 200℃
üA neutral layer is required to attain perpendicular pattern formation
üNumber of defects (as of 2014): 24/cm2
PS-b-PMMA: NL
neutral layer
top-coat layer
neutral layer
- Monomers are deliberately designed to afford the unique interactions developing sub-10nm morphologies
- Low Tg of novel BCPs allows structure formation exclusively by thermal annealing
- Novel BCPs show intrinsic long range ordered structure due to high effective χ
- Unique structural features of BCPs render perpendicular pattern formation on a substrate without any surface modification
- Novel BCPs are applicable to graphoepitaxy DSA processes
§ LG novel BCPs generate perpendicular sub-10nm patterns without surface modification ofsilicon substrate
LG Novel BCP
: No neutral layer, No top-coat
High χ BCP
: NL+ top-coat
spin coating brushand annealing
removingexcess brush
spin coating BCP
directed self-assembly
PS-b-PMMA Process
LG Flow
: Additional processes to construct a neutral layer are necessary
: No additional process is necessary for a DSA, presenting a much simpler process
lithography spin coating BCP directed self-assemblysilicon wafer
§ Novel BCPs facilitate the more simple process compared to the conventional chemoepitaxy
crosslinking matmaterial
lithography breakthroughetching
trim etching stripping photoresist
Hydrophobic HydrophilicHydrophilic
water contact angle=85°: silicon wafer coated with Cu
water contact angle=40°: bare silicon wafer
water contact angle=15°: O2 plasma-treated silicon wafer
top surface SEM top surface SEM top surface SEM
50nm 50nm 50nm
cross-section TEM cross-section TEM cross-section TEM
§ Pattern formation is unaffected by substrate surface conditions
: Structures by novel BCPs show perpendicular lamellae orientation regardless of substrate surface properties
§ LG novel BCPs were synthesized successfully by conventional polymerization
GPC
A-B BCPA block
12 15 18 21
12
15
18
21
Mn
L0
A block B block
Mn fB Lo
BCP1 21.6k 0.48 19.8nm
BCP2 18.9K 0.43 17.5nm
BCP3 15.4k 0.55 14.2nm
BCP4 13.2k 0.56 11.6nm
BCP5 17.8k 0.31 17.4nm Mn
Ø The monomers A and B are designed to induce intermolecular interactions
ØGPC data verify the successful synthesis of BCPs with narrow PDIs
ØSeries of BCPs with diverse Mn and volume fractions were readily prepared
ØA linearly fitted Mn to Lo plot reveals a fully stretched BCP architecture
Ø Perpendicular pattern formation without the aid of a neutral layer or top-coating
Ø Pattern formation is unaffected by substrate surface condition
Ø Realization of sub-10nm patterns of tunable size and morphology
Ø Novel BCPs facilitate the more simple DSA process compared to the conventional chemical epitaxy
ü Development of a new BCP capable of structure formation of broad pitch sizes and hole pattern
top surface SEM top surface SEM top surface SEMFT FT FT
50nm
top surface SEM top surface SEM
50nm
cross-section TEM
BCP1; Lo=19.8nm BCP3; Lo=14.2nm BCP4; Lo=11.6nm
§ Realization of sub-10nm patterns of tunable size and morphology
: Line patterns of around 5~10 nm line width are routinely generated within BCP thin films
: Dot patterns of ~20nm pitch, 7.5nm diameter are routinely generated within BCP thin films
BCP5; Lo=~20nm
BCP2; Lo=17.5nm Thickness: 40nmTrench: W=160nm/M=140nm /D=40nm
BCP1; Lo=19.8nmThickness : 25nm Thermal annealing: 160℃, 5min
top surface SEM
cross section SEM
100nmcross section TEM
As-spun
5min
50nmTEM
50nmTEM
- On bare substrates : perpendicular lamellar pattern
- In trenched substrates : perpendicular lamellar pattern
- Perpendicular lamellar pattern formation is originated from the top surface
§ Perpendicular pattern formation without the aid of a neutral layer or top-coating
50nmTEM
50nmTEM
