ALD high-k and higher-k integration on GaAs

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ALD high-k and higher-k integration on GaAs Ozhan Koybasi 1), Min Xu 1), Yiqun Liu 2), Jun-Jieh Wang 2), Roy G. Gordon 2), and Peide D. Ye 1)* 1) School of Electrical and Computer Engineering, Purdue University, West Lafayette, Indiana, U.S.A. 2) Department of Chemistry and Chemical Biology, Harvard University, Cambridge, Massachusetts, U.S.A. *Email: yep@purdue.edu Silicon-based CMOS devices with traditional structures are approaching fundamental physical limits. Researchers are looking for ways to continue the trend of scaling by using alternative materials such as Ge and III-V compound semiconductors that could out-perform Sibased CMOS. Although significant progress is made on InGaAs MOSFETs with ALD high-k dielectrics (Al 2 O 3, HfO 2, HfAlO, and ZrO 2 ), GaAs MOSFETs remain a big challenge, mostly showing minuscule drain currents. In this paper, we report on the strong dependence of the electrical properties on different GaAs surface orientations. (111)A Ga polar surface is much more forgiving in terms of Fermi-level pinning for n-channel GaAs MOSFET as shown in Fig.1, compared to (100) Ga-As non-polar surface. It might be directly related with ALD surface chemistry and could be explained by the trap neutral level model. In order to further scale down the equivalent oxide thickness (EOT) of dielectrics, the integration of ALD higher-k (LaLuO 3 ) on GaAs was systematically studied. The precursors lanthanum tris(n,n'-diisopropylformidinate), and lutetium tris(n,n'-diethylformamidinate) reacted with water vapor at 350 o C. The dielectric structures are shown in Fig.2. Fig. 3 shows multi-frequency CV characteristics on n-type and p- type MOS capacitors on GaAs (100) surface with 2 nm Al 2 O 3 /8 nm LaLuO 3 / as composite dielectric (structure A in Fig. 2). The observed frequency dispersion at accumulation capacitance is comparable to that of pure ALD Al 2 O 3. Meanwhile, LaLuO 3 with k = 25 to 30 provides a significant advantage in capacitance values. The work verifies the potential to integrate ALD higher-k dielectrics on III-V and deliver 1-2 nm EOT dielectrics by ALD for aggressively scaled ultimate CMOS technology. (A) (B) (C) (D) Drain Current I DS (ma/mm) 16 14 12 10 8 6 4 2 0 ALD Al 2 O 3 (8nm)/GaAs (111)A V GS from 0V to 5.5V in steps of 0.5V L CH =0.75 µm 0.0 0.5 1.0 1.5 2.0 Drain Voltage V DS (V) 2nm Al 2 O 3 2nm Al O GaAs n-type or p-type (100) or (111)A 2nm Al 2 O 3 2nm Al 2 O GaAs 2 3 3 n-type or p-type (100) or (111)A GaAs n-type or p-type (100) or (111)A GaAs n-type or p-type (100) or (111)A Figure 2 Four LaLuO 3 higher-k dielectric structures on GaAs. Capacitance (F) 8.00E-011 7.00E-011 6.00E-011 5.00E-011 4.00E-011 3.00E-011 p-gaas(100) substrate PDA@600 o C,30s 500Hz 10KHz 100KHz As-deposited 500Hz 10KHz 100KHz Capacitance (F) 8.00E-011 7.00E-011 6.00E-011 5.00E-011 4.00E-011 3.00E-011 2.00E-011 n-gaas(100) substrate PDA@600 o C,30s 500Hz 10KHz 100KHz As-deposited 500Hz 10KHz 100KHz Figure 1 I-V characteristics of an NMOSFET on GaAs (111)A surface with 8nm ALD Al 2 O 3 as gate dielectric. 2.00E-011 1.00E-011-5 -4-3 -2-1 0 1 2 3 4 Gate Voltage (V) 1.00E-011 0.00E+000-4 -3-2 -1 0 1 2 3 4 5 Gate Voltage (V) Figure 3 Multi-frequency CV of p-type and n-type GaAs MOS capacitors with the process splits of as-grown and 600 o C post -deposition anneal (PDA). The diameter of the capacitors is 100μm.

ALD high-k k and higher-k k integration on GaAs O. Koybasi 1, M. Xu 1, Y. Liu 2, J.-J. Wang 2 RG R.G. Gordon 2 and P.D. Ye 1 1. School of Electrical and Computer Engineering, g, Purdue University 2. Department of Chemistry and Chemical Biology, Harvard University The ALD 39 2009 th IEEE SISC 2008.12.11 7. 20. 2009 Ye s Group, ECE

Outline Motivation Brief results on ALD Al 2 O 3 /GaAs(111)A MOSFET ALD Higher-k LaLuO 3 deposition process ALD Higher-k k LaLuO 3 on GaAs (111)A and (100) surfaces --- 4 different MIS structures are used to investigate Summary

Motivation 1. Traditional III-V: high frequency and/or high power applications; New III-V thrust: high performance logic applications Si based CMOS scaling is going to be end in 2015. For 22 nm technology node beyond, it requires novel channel materials such as III-V and high-k 2. The advantage of III-V as channel materials is high electron mobility. 3. Advantage of ALD high-k: --- commercial ALD tools are available --- ALD self-cleaning effect on III-V --- significant progress on III-V MOSFET in the past 3-5 years using ALD --- easy transfer to Si CMOS platform Si MOSFET (Intel) Si strained Si bulk Ge GaAs GaN InP In0.53Ga0.47As InAs InSb μe 400 1,000 3,900 8,500 1,250 5,400 8,000 20,000 30,000 μh 160 240 1,800 400 850 200 300 500 800 Eg (ev) 1.1 1.1 0.66 1.42 3.4 1.35 0.72 0.36 0.18

Inversion GaAs MOSFET: A Historical Dilemma Most of inversion GaAs NMOSFETs have minuscule drain current ( < 1 ma/mm). F Ren et al Solid State Electronics 41 1751 (1997) - F. Ren et al. Solid-State Electronics 41, 1751 (1997) - Y. Xuan et al. Appl. Phys. Lett. 88, 263518 (2006) - D. Shahrjerdi et al. Appl. Phys. Lett. 92, 203505 (2008) - any many others in 70s and 80s. New Solution : our results on GaAs(111)A (next slide) Alternatives: (1) In-rich InGaAs (see recent work by Purdue, Intel, IBM, NTHU, UCSB ) Potential issue: narrow bandgap material, band-to-band tunneling, (2) Si interfacial control layer or SiH 4 passivation on GaAs (see recent work by UT Austin, Intel, SUNY Albany, IBM, NUS, UT Dallas,.) Potential ili issue: additional i SiO 2 increases EOT, inversion i mechanism unclear,

Inversion NMOSFET on GaAs(111)A with Al 2 O 3 5 4 V GS 0~4V in steps of 0.5V x 10-4 GaAs(100) Lg=4 m ( A/ m) 3 2 1 Drain Current I DS 0 0.0 0.5 1.0 1.5 2.0 Drain Voltage V DS (V) I DS =3.5x10-4 A/ m GaAs (100) X100,000 (111)A Ga polar (100) Ga-As un-polar Explained by an empirical model Based on trap neutral level shift 36 30 24 18 12 6 0 V GS 0~4V in steps of 0.5V GaAs(111)A Lg=4 m GaAs (111)A 00 0.0 05 0.5 10 1.0 15 1.5 20 2.0 Drain Voltage V DS (V) [* M. Xu et al, APL, 94, 212104, 2009] I DS =30 A/ m [* W.E.Spice Peter s al, Group, JVST, 16(5), School 1979] of ECE Drain Current I DS ( A/ m)

Higher-k on GaAs for EOT scaling Further application limited due to the small k value (8~9) of Al 2 O 3 Implementation of higher-k gate dielectric LaLuO 3 with k=24~26!!! Questions: How to integrate higher-k LaLuO 3 on GaAs or III-V? Is it feasible to integrate LaLuO 3 directly on GaAs?

Higher-k dielectric deposition process H 2 O Furnace Heater N 2 Pump 120 o C La Lu 115 o C La 2 O 3 : Lu 2 O 3 Deposition temp. MO precursors Oxidant Bubbler temp. 350 o C 1:1 120 o C for La 115 o C for Lu La(amd) 3 DI H Lu(amd) 2 O 3 [* provided by Y. Liu in Prof. Roy Gordon s group at Harvard]

Requirements for higher-k integration (4) Metal Electrode Higher-k Compatible? GaAs Different MIS structures to be studied each structure splits into two: as-deposited PDA@600 o C,30s in N 2 Ni Gate Ni Gate Ni Gate GaAs(111)A or (100) GaAs(111)A or (100) GaAs(111)A or (100) (1) (2) (3)

C-V characteristics on p-type GaAs 200 160 w/ PDA as-deposited (pf) Ni Gate Frequencies: 120 80 Capacitance GaAs(111)A or (100) 500Hz 10KHz 100KHz 40-5 -4-3 -2-1 0 1 2 3 4 5 4 3 2 1 0 1 2 3 4 Gate Voltage (V) Capacitance increased after annealing due to water-adsorptive property of La-based dielectric All p-type GaAs MOS CVs are good-looking with less frequency-dispersion at accumulation, which includes (100), (111)A with Al 2 O 3, HfO 2, HfAlO and LLO. It relates with ALD self-cleaning effect on As 2 O 3, As 2 O 5, (see Frank et al. 2005, Huang et al. 2005, Hinkle et al. 2007, and others) and lower half band-gap of GaAs has less The problem. 39 th IEEE SISC 2008.12.11

C-V characteristics on Structure (1) 160 120 80 w/ /PDA as-deposited Capacitance (pf) Ni Gate Frequencies: 500Hz 10KHz 100KHz 40 n-gaas(100) -4-3 -2-1 0 1 2 3 4 5 0 500Hz Gate Voltage (V) 160 120 w/ PDA as-deposited Capacitance (pf) GaAs(111)A or (100) EOT: ~3.3nm Frequency dispersion on (111)A is better than that on (100) Lower D it along upper half band-gap of GaAs(111)A EOT~3.3nm, k value is extracted to be ~24 80 40 n-gaas(111)a -4-3 -2-1 0 1 2 3 4 5 Gate Voltage (V)

C-V characteristics on Structure (2) 200 w/ PDA as-deposited 160 120 80 40 Capacitance (pf) Ni Gate 160 n-gaas(100) -4-3 -2-1 0 1 2 3 4 5 0 Gate Voltage (V) 240 w/ PDA as-deposited 200 Capacitance (pf) GaAs(111)A or (100) EOT: ~2.3nm 120 80 40 n-gaas(111)a -4-3 -2-1 0 1 2 3 4 5 Gate Voltage (V) Capacitance increased as expected and EOT scaled down to 2.3nm Exactly due to the removal of Al 2 O 3 capping layer of 1nm EOT No additional interface layer introduced by metal/higher-k direct contact

C-V characteristics on Structure (3) Ni Gate Ni Gate GaAs(111)A or (100) GaAs(111)A or (100) 280 240 200 160 w/ PDA as-deposited 240 w/ PDA as-deposited 200 160 e (pf) Capacitanc ce (pf) 120 80 apacitanc C40 n-gaas(111)a -4-3 -2-1 0 1 2 3 4 5 120 80 40 n-gaas(111)a -4-3 -2-1 0 1 2 3 4 5 Gate Voltage (V) Gate Voltage (V) Surprisingly, capacitance didn t obviously increased after annealing Some interfacial layer may be introduced at higher-k/gaas interface Will this extra-layer influence the interface quality?

Interface Trap Density on GaAs(111)A 35 30 25 20 15 10 5 0 Al 2 O 3 /n-gaas(111)a (control) Al 2 O 3 /LaLuO 3 /n-gaas(111)a (3) Al 2 O 3 /LaLuO 3 /Al 2 O 3 /n-gaas(111)a (1) (1~3)X10 11 Dit 2 cm -2 ev -1 (x1012 ) 0.6 0.8 1.0 1.2 E-E v (ev) D it was extracted by HF-LF method (3) almost has the same D it as the control sample, but has higher D it to the E C edge Surprisingly even with Al 2 O 3 ICL, (1) has higher D it than (3)

Pure higher-k direct on GaAs No reasonable C-V characteristic obtained!!! Metal Electrode Higher-k GaAs Possible Problems: Two interfaces shows good quality respectively, Why doesn t it work with pure higher-k direct on GaAs? Small conduction band offset?? Further investigation needed!!!

Summary Inversion NMOSFET is realized by integration of ALD Al 2 O 3 on GaAs(111)A Higher-k k LaLuO 3 is first demonstrated to be integrated on GaAs --- metal/laluo 3 interface quite stable --- Al 2 O 3 /LaLuO 3 /GaAs has comparable interface as Al 2 O 3 /GaAs --- Al 2 O 3 /LaLuO 3 /GaAs interface may introduce additional layer after PDA Further study on metal/laluo 3 /GaAs is needed We acknowledge the valuable discussions and on-going collaboration with Prof. R.M. Wallace s group at UT Dallas. The work is partly supported by NSF, SRC FCRP MSD Center, and DoD ARO.

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