N-Vinylpyrrolidone-vinyl acetate block copolymers as drug delivery ...
Functional Polymer/1 Semester, 2006 Part II. Functional ... · Functional Polymers for...
46
Prof. Jin-Heong Yim Functional Polymer/1 st Semester, 2006 _________________________________________ Part II. Functional Polymers for Semiconductor Applications Outline of Part Polymeric Insulator for Semiconductor Applications Introduction of Silicone Chemistry Theory of Sol-Gel Chemistry Organic-Inorganic Hybrid Polymer Semiconductor Insulating Materials Nanoporous Polysiloxane Materials Summary of Future Trends
Transcript of Functional Polymer/1 Semester, 2006 Part II. Functional ... · Functional Polymers for...
Prof. Jin-Heong Yim
Functional Polymer/1st Semester, 2006_________________________________________
Part II. Functional Polymers for Semiconductor Applications
Outline of PartPolymeric Insulator for Semiconductor Applications
Introduction of Silicone ChemistryTheory of Sol-Gel ChemistryOrganic-Inorganic Hybrid PolymerSemiconductor Insulating MaterialsNanoporous Polysiloxane MaterialsSummary of Future Trends
Prof. Jin-Heong Yim
Hybrid Organic-Inorganic Materials
Prof. Jin-Heong Yim
Why HOIM??
Prof. Jin-Heong Yim
Classification of HOIM
Prof. Jin-Heong Yim
Approach of HOIM
Prof. Jin-Heong Yim
Organic-Inorganic Hybrid Materials
◆ Homogeneous SystemHomogeneous System::
from monomer or miscible systemfrom monomer or miscible system
◆ Heterogeneous SystemHeterogeneous System::
Phase separated system with domainPhase separated system with domain~~μm
◆ Preparation routePreparation routeSolution mixing, Solid state RXN, Solution mixing, Solid state RXN,
SolSol--Gel Process, InGel Process, In--situ polymerizationsitu polymerization
Prof. Jin-Heong Yim
SiO
SiO
SiO
SiO
SiOH
SiO
SiO
SiO
SiO
SiOH
O O O O
R R R R
R R R R
Ladder structure;∗ High thermal stability∗ High Tg.∗ Low viscosity
∗ High thermal stability∗ High Tg.∗ Low viscosity
Pendant group∗ Excellent thermal stability∗ Low moisture absorption∗ Low conductivity/ Low dielectric constant∗ Good hardness
∗ Excellent thermal stability∗ Low moisture absorption∗ Low conductivity/ Low dielectric constant∗ Good hardness
End group(Si-OH);
∗ Thermoset (120 – 350oC)∗ Versatility to organic reaction
∗ Thermoset (120 – 350oC)∗ Versatility to organic reaction
Si-O-Si bond;∗ Optical transparency∗ Oxygen plasma resistance∗ Compatibility with inorganic material
∗ Optical transparency∗ Oxygen plasma resistance∗ Compatibility with inorganic material
Organic Inorganic Hybrid System: SSQ
Prof. Jin-Heong Yim
Nomenclature I
OMeSi
MeO OMeOMe
MeSi
MeO OMeOMe
MeSi
MeO MeOMe
MeSi
MeO MeMe
“Q” “T” “D” “M”
Hardness/Modulus Increase
Toughness IncreasePolarizability Decrease
Prof. Jin-Heong Yim
“Q” Structure
Molecular Structure
“T” Structure “D” Structure
Prof. Jin-Heong Yim
Nomenclature IIT : Tri-functional groupi : The number of oxygen bridging atoms (0~3)
T3RSiO3/2
T2RSiO2OH
T1RSiO(OH)2
T0RSi(OH)3
Nomen-clature
FormulaStructure
O SiR
OO
HO SiR
O
O
HO SiR
OHO
HO SiR
OHOH
HO SiR
OHOH
T0
T3T2 T1
Si
R
O
OH Si
R
O
O Si
R
OH
SiSiSi O O O Si
O Si
O
R
O
OH
RRRR
Si
OH
R
OH
HO HO
Prof. Jin-Heong Yim
Si
CH3
O
O Si
CH3
O Si
O
O Si
CH3
O
SiSiSiSi
CH3
O
CH3 CH3 CH3
Si
CH3
O
Si
CH3
CH3
CH3
CH3
CH3
CH3
Si O
CH3
CH3
Si
CH3
CH3
O Si
CH3
CH3
O Si
CH3
CH3
O Si
CH3
CH3
O Si
CH3
CH3
Si
CH3
CH2
O Si
CH3
CH3
CH2
Si
CH3
O Si
CH3
CH3
O
O Si
CH3
CH2
CH2
Si
CH3
O Si
O Si
CH3
CH3
CH3
CH3
O
O Si
CH3
CH2
CH2
Si
CH3
Silicone resinSilicone resin
Silicone Ladder PolymerSilicone Ladder PolymerPolyorganosilsesquioxanePolyorganosilsesquioxane (SSQ)(SSQ)
Silicone RubberSilicone Rubber
Silicone OilSilicone Oil
R = CH3, Ph etc
HO Si
R
O
O Si
R
O
O Si
R
O
SiSiSiHO O O O Si
O Si
O
R
O
O
RRRR
Si
Si
O
R
OH
OH
R
S i
O
O S i
O
O S i
O
S iS iS i O O O S i
O S i
O
O
O
OOOO
S i
S i
O
O
S i O S i O S i O S i O S i
Silica glassSilica glass
Various Silicone Structure
Prof. Jin-Heong Yim
∗ Ladder-like Polymer or with defects structureor with random structure
∗ Branched Ladder Polymer∗ Cured Ladder Polymer∗ Perfect Ladder Polymer
Structures
Pendant group∗ Methyl(Polymethylsilsesquioxane;PMSQ)∗ Phenyl(Polyphenylsilsesquioxane;PPSQ)∗ Protone(Polyhydrogensilsesquioxane;PHSQ)
Silicone modified organic polymer
∗ Alkyl∗ Epoxy∗ Polyester∗ Phenol∗ Acrylic
Proposed applications:Optics,adhesives,abrasive resistant coating etc
Si
R
O
OH Si
R
O
O Si
R
OH
SiSiSi O O O Si
O Si
O
R
O
O
RRRR
Si
Si
O
R
R
HO HO
T2 T3
Functionality Control
Prof. Jin-Heong Yim
Recent Publications
Prof. Jin-Heong Yim
Sol-Gel process
RO Si
R
OR
OR RO Si
R
OH
OR RO Si
R
OH
OH HO Si
R
OH
OH
RO Si
R
OR
OSi RO Si
R
OH
OSi HO Si
R
OH
OSi
SiO Si
R
OR
OSi HO Si
R
OSi
OSi
SiO Si
R
OSi
OSi
HYDROLYSIS
CONDENSATION
Prof. Jin-Heong Yim
Sol-Gel process
Again condensation table place before the completion of hydrolysis
Brinker and Scherer, “Sol-Gel Science, The Physics and Chemistryof Sol-Gel Processing”, Academic Press, San Diego (1990).
Si OR Si OH
HO Si Si O Si
+ H2OHydrolysis
Si OR + + ROH
+ ROHEsterification
Alcohol condensation
Alcoholysis
HO Si Si O SiSi OH + + H2OWater condensation
Hydrolysis
Prof. Jin-Heong Yim
Homogeneous System
Prof. Jin-Heong Yim
Organic Functional Groups
Prof. Jin-Heong Yim
Porosity Control
Prof. Jin-Heong Yim
Optical Property Control
PorphyrinsPorphyrins
TriarylaminesTriarylamines
OligothiopheneOligothiopheneTerphenyleneTerphenylene
Prof. Jin-Heong Yim
Mechanical Control
Prof. Jin-Heong Yim
Metal bearing bridging group
Prof. Jin-Heong Yim
Heterogeneous System
◆ Hydrogen bond InteractionHydrogen bond Interaction
◆ π-π bond Interactionbond Interaction
◆ Ionic interactionIonic interaction
POZO ; Poly(2POZO ; Poly(2--methylmethyl--22--oxazoline)oxazoline)PVP ; Poly(NPVP ; Poly(N--vinylpyrrolidone)vinylpyrrolidone)PDMAA; Poly(N,NPDMAA; Poly(N,N--dimethylacrylamide)dimethylacrylamide)
Prof. Jin-Heong Yim
Hydrogen Interaction
Prof. Jin-Heong Yim
Hybrid system
◆ More homogenous systemMore homogenous system
Organic monomer (DMAAm)Organic monomer (DMAAm)
Inorganic monomerInorganic monomer
Radical polymerizationRadical polymerization
SolSol--Gel RXNGel RXN
HybridHybrid
◆ IPN systemIPN system
Organic monomer Organic monomer (DMAAm&MBAAm or Styrene&DVB)(DMAAm&MBAAm or Styrene&DVB)
Inorganic monomerInorganic monomer
Radical polymerizationRadical polymerization
SolSol--Gel RXNGel RXN
HybridHybrid
DMAAm; (CHDMAAm; (CH22=CHCON(CH=CHCON(CH33))22), MBAAm; (CH), MBAAm; (CH22=CHCONH)=CHCONH)22CHCH22
Prof. Jin-Heong Yim
π-π bond Interaction
◆ Hydrogen bond InteractionHydrogen bond Interaction
◆ π-π bond Interactionbond Interaction
◆ Ionic interactionIonic interaction
Prof. Jin-Heong Yim
Ionic interaction
◆ Hydrogen bond InteracHydrogen bond Interac
◆ π-π bond Interactionbond Interaction
◆ Ionic interactionIonic interaction
Prof. Jin-Heong Yim
Semiconductor Insulating Materials
Prof. Jin-Heong Yim
Semiconductor Insulating MaterialsDevice performance is parasitized by RC delayDevice performance is parasitized by RC delay
in the case of deep subin the case of deep sub--micron devicesmicron devices
Prof. Jin-Heong Yim
ITRS Roadmap
Prof. Jin-Heong Yim
Insulating MaterialsInsulating Materials
Requirement
CVD Spin-on
Organic Organo silicate Organic Organo silicate
Parylene (2.5)Polynaphthalene
(2.4)
SiO2 (4.0)SiOF (3.5)SiOC(2.7)
BCB (2.7)FLARE (2.8)
Polyimide (2.7)Polyphenylene
(2.65)Teflon (2.3)
HSQ (3.1)MSQ (2.7)
Xerogel (~2.0)Aerogel (~2.0)
- Good Gap-fill (for Al interconnection) - Metal Corrosion Resistance- Good Thermal Stability (> 500oC) - Water Resistance- Good Adhesion - No issue for integration- No Crack (Mechanical Strength)
Prof. Jin-Heong Yim
Intergration Issues
Prof. Jin-Heong Yim
Considering Parameters
Prof. Jin-Heong Yim
Mechanical Properties
Prof. Jin-Heong Yim
Si O SiO O
Si SiO
O O
OO
Si Si
SiSiO O
RR
RRO
RR
R R OO Si O Si O Si O Si O
O Si O Si O Si OH
O OO
SiO
R
HO
R R R
R R RHO
R{ } {}{
}
{
xy
z
R
SiX
X
X
R=CH3, HX=OMe, OEt, Cl
Hydrolysis Condensation
nanopore
: as a precursor for sol-gel-drived polymer thin film
Typical SSQ Polymer
Prof. Jin-Heong Yim
Spin Coating Process
Spin Coating
Hot Plate Bake
Furnace Cure
Hot plate
Wafer
Prof. Jin-Heong Yim
CVD Deposition
Conventional (plasma type)
TEOS + CF4 ---> FSG
Prof. Jin-Heong Yim
Sol-Gel Process (Aerogel, Xerogel)
Spin -coat (Sol)
Wet (Sol)
Dried Film
Aging
Drying
Prof. Jin-Heong Yim
PorogenPorogen--templatedtemplated Approach Approach
Decomposition
Nanohybrid Nanofoam
Polymer Inorganic material
keffective = Vmatrix × kmatrix + Vair × kair ( =1.0)
Porogen = Pore Generating Material
(as matrix)(as porogen)
Prof. Jin-Heong Yim
Integration Scheme : Al Integration Scheme : Al 배선배선 공정공정
Al Al Al
Si
SiO2Al Al Al
Si
SiO2
Low-k
SiO2
Al Al Al
Si
SiO2
W
- Deposit Al
- Anneal Al
- Pattern Al
- Deposit & Cure Low-k
- Deposit cap
- Pattern Via
- Deposit W
Prof. Jin-Heong Yim
Integration Scheme : Al 배선 공정
Al Al Al
Si
SiO2
W
Al Al Al
Si
SiO2
W- CMP W
- Deposit Al
-Al anneal (>400 C)
-Pattern line
- Deposit and Cure Low-k
- Deposit Cap
Prof. Jin-Heong Yim
Problems vs.Requirements
- Inadequate gapfill
- Cracking after thermal cycling
- Delamination
- Deformation of low-k layer with compressive capping layers
- Outgassed Via
- Good gapfill Properties
- Good thermal Stability/Good Crack resistance
- Good Adhesion/small CTE mismatch
- Good mechanical Strength/High Tg
- Little outgassing
Problems Property Requirements
Prof. Jin-Heong Yim
Integration Scheme : Damascene 공정
Al
Si
SiO2SiN
Low-kSiO2
Al
Si
SiO2SiN
SiO2
1. Deposit
2. Deposit Cap3. Pattern and etch low-k
Prof. Jin-Heong Yim
Integration Scheme : Damascene 공정
Al
Si
SiO2
Cu
Al
Si
SiO2
SiN
4. Deposit barrier
5. Deposit Cu Seed
6. Electroplated Cu
7. Cu anneal (250-350 C)
8. CMP
9. Deposit Cap
Prof. Jin-Heong Yim
Problems vs.Requirements
Problems
-Delamination
- Etch Selectivity to Photoresist/PR strip/wet Cleans
- Outgassed in via
- Mechanical strength
- Dry etch issue in some low-k
Property Requirements
- No Gapfill needed
- Good thermal Stability
- Good Adhesion/small CTE mismatch
- Good mechanical Strength/High Tg
- Little outgassing
- Good crack resistance
Prof. Jin-Heong Yim
Material Structure-Property Relationships
♦ Bond polarizability affect the dielectric constant and thermal stability
Bond Polarizability (Å3) Bond Energy (kcal/mol)
C-C 0.531 83
C-F 0.555 116
C=O 1.020 176
C=C 1.643 146
♦ C-F bonds lower k.
C=O and C=C bonds improve thermal stability, but both increases k.
♦ O-H bonds increase k, and faciliate moisture uptake which also
increases k.
Prof. Jin-Heong Yim
CH3
Si
O
Si
CH3
n
CH3
Si O
O
Si O
CH3
Si O
O
Si OH
OH
OT ! T ! Like Like SilsesquioxaneSilsesquioxane (Stability)(Stability)
D ! D ! As an As an ElastomerElastomer
((Increase Toughness & ModulusIncrease Toughness & Modulus))Alkyl bridge !Alkyl bridge !Increase molecular porosity (decrease k)Increase molecular porosity (decrease k)Good mechanical propertiesGood mechanical properties
SiSi--OH group !OH group !Compatibility with Compatibility with porogenporogenmoisture absorption moisture absorption CrossCross--LinkingLinkingGood Mechanical PropertiesGood Mechanical Properties
Example of SSQ precursor
