Selective Atomic Layer Deposition of TiO 2 on Silicon/Copper-patterned Substrates UIC REU 2011 AMReL, University of Illinois at Chicago Abigail Jablansky Department of Chemical and Biomolecular Engineering, University of Pennsylvania
Dec 16, 2015
Selective Atomic Layer Deposition of TiO2 on Silicon/Copper-
patterned Substrates
UIC REU 2011
AMReL, University of Illinois at Chicago
Abigail JablanskyDepartment of Chemical and Biomolecular Engineering,
University of Pennsylvania
What is ALD?• Atomic layer deposition• Method:
– Precursor (TDEAT)– Purge (N2)– Oxidant (H2O)– Purge (N2)
• Batch adsorption process• Easily controlled but
time-consuming• Characterized with ellipsometry,
X-ray photoelectron spectroscopy(XPS)
• Diverse applicationswww.cambridgenanotech.com/ald
Copper and Silicon
• Conductive substrate• Small channels of
conduction in microelectronics
• Need a thin barrier layer on silicon
• Copper oxidizes more easily– Selective ALD (SALD)– Native oxide
www.electroiq.com
Native Oxides• Prevention
– Self-assemblingmolecules1
• Minimization– Limited air exposure2
– Few cycles3
• Reduction– GaAs oxide remains under
HfO2 but converted under Al2O3
4
Tao, Q.; Jursich, G.; Takoudis, C. App. Phys. Lett. 2010, 96, 192105
1Chen, R.; Kim, H.; McIntyre, P.C.; Bent, S.F. Chem. Mater. 2005, 17, 536.2Lee, H.D.; Feng, T.; Yu, L.; Mastrogiovanni, D.; Wan, A.; Gustafsson, T.; Garfunkel, E. App. Phys. Lett. 2009, 94, 222108.3Tao, Q.; Overhage, K.; Jursich, G.; Takoudis, C. Submitted to Journal of Physi Chem. C. 2011.4Frank, M.M.; Wilk, G.D.; Starodub, D.; Gustafsson, T.; Garfunkel, E.; Chabal, Y.J.; Grazul, J.; Muller, D.A. App. Phys. Lett. 2005, 86, 152904.
Copper Oxides
• Cu2O (cuprous oxide)– Linear– Most stable copper
compounds at high T
– Forms ammine under NH3
5
• CuO (cupric oxide)– Square planar– Decomposes at
high T to Cu2O + O2
– H2 or CO reduction at 250oC5• Cu2O forms first, then CuO if stable6
• Reduction methods
5Cotton, F.A.; Wilkinson, G. Advanced Inorganic Chemistry, 2nd ed. New York: Interscience Publishers, 1966, pp.894-902.6Zhu, Y.; Mimura, K.; Lim, J.; Isshiki, M.; Jiang, Q. Metal. and Mineral Trans. A. 2006, 37A, 1231.
Project Description
• ALD of TiO2 onto Si/Cu wafers– Precursor: tetrakis(diethylamino)titanium (TDEAT)– Oxidizer: water
• Compare 24-hr Cu (1 nm native oxide) exposure to 1-hr7
• Minimize exposure from reactor to ellipsometer, x-ray photoelectron spectroscopy (XPS)
7Tao, Q. PhD Dissertation, University of Illinois at Chicago, 2011.
Reactor Schematic
Ice bath
Hot wall reactor
Tao, Q. PhD Dissertation, University of Illinois at Chicago, 2011.
Experimental Setup
Characterization
Ellipsometry
• Reflects light off thin films• Measures polarization
after reflection
X-ray photoelectron spectroscopy (XPS)
• X-rays are energy source• Measures kinetic energy,
number of escaping electrons
Results• Verified Tao’s work7
– Constant growth rate = linear growth
0 5 10 15 20 25 30 350
5
10
15
20
25
30
f(x) = 0.858713450292395 xR² = 0.956743860444266
Thickness of TiO2 on Si
Number of cycles
Th
ickn
ess
(A)
7Tao, Q. PhD Dissertation, University of Illinois at Chicago, 2011.
Troubleshooting• Temperature
– Increases along path to reactor– Keep oxidizer cold
• Pressure– “Resting pressure” around 0.176 torr– Cycles during deposition
• N2 tank, H2O level in bubbler
• Check ellipsometer• Precursor level, clogged pipes
Results (cont.)
The colors could represent a deposition layer thickness profile or a chemical vapor deposition (CVD).
Summary
• Objective: SALD of TiO2 on Si for microelectronic applications
• Method: reduce native oxide on Cu– Minimize air exposure (in progress)– In situ reduction (future work)
• Characterization: ellipsometry, XPS• Results to date verify prior research• Not enough data to conclude about TiO2 on copper
• Troubleshooting, design setbacks are important parts of engineering
Acknowledgements
• National Science Foundation, EEC-NSF Grant # 1062943
• CMMI-NSF Grant # 1134753• Jorge I. Rossero A.• Runshen Xu• Arman Butt• Dr. Jursich• Dr. Takoudis
References
•Chen, R.; Kim, H.; McIntyre, P.C.; Bent, S.F. Chem. Mater. 2005, 17, 536.•Lee, H.D.; Feng, T.; Yu, L.; Mastrogiovanni, D.; Wan, A.; Gustafsson, T.; Garfunkel, E. App. Phys. Lett. 2009, 94, 222108.
•Tao, Q.; Jursich, G.; Takoudis, C. App. Phys. Lett. 2010, 96, 192105•Tao, Q.; Overhage, K.; Jursich, G.; Takoudis, C. Submitted to Journal of Phys. Chem. C. 2011.
•Frank, M.M.; Wilk, G.D.; Starodub, D.; Gustafsson, T.; Garfunkel, E.; Chabal, Y.J.; Grazul, J.; Muller, D.A. App. Phys. Lett. 2005, 86, 152904.
•Cotton, F.A.; Wilkinson, G. Advanced Inorganic Chemistry, 2nd ed. New York: Interscience Publishers, 1966, pp.894-902.
•Zhu, Y.; Mimura, K.; Lim, J.; Isshiki, M.; Jiang, Q. Metal. and Mineral Trans. A. 2006, 37A, 1231.
•Tao, Q. PhD Dissertation, University of Illinois at Chicago, 2011.•Falkenstein, Z.; Hakovirta, M.; Nastasi, M. Thin Solid Films. 2001, 381, 84.•Tompkins, H.G.; Allara, D.L. J. Colloid and Interface Science. 1974, 49, 410.•Sakata, Y.; Domen, K.; Maruya, K.-I.; Onishi, T. Appl. Spec. 1988, 42, 442.