在半導體製程微縮的過程中，除了水平方向的縮減外，垂直方向也必須作等比例縮減來維持元件的基本操作。所以在45及32奈米時代，傳統的二氧化矽絕緣層厚度將需要縮小到約奈米左右，此時閘極之電子藉由穿隧(Tunneling)效應通過閘極氧化層流入元件之汲極，產生元件之大量漏電流及遷移率下降問題。為了降低閘極漏電流，必須將閘極絕緣層的實際厚度增加以減少穿隧電流，但是又要維持在電性操作時之等效氧化層厚度(Effective Oxide Thickness; EOT)不變。於是使用高介電常數(k)材料作為絕緣層，以同時兼顧閘極絕緣層實際厚度與電性等效厚度便成為眾所矚目之課題。尤其二氧化鉿（HfO2）於最近幾年為研究最廣之高介電材料。
氧化鉿可直接成長在矽晶片上擁有絕佳的熱穩定性、較高的介電係數、相對大的能隙寬度，但同時超薄氧化鉿面臨到了電子遷移率下降、大量的固定電荷、臨界電壓的不穩定等問題仍須解決，許多學者已證實透過添加材料(矽、鋁、氮、鈦、鉭)來改善氧化鉿所遭遇的問題，但必須考量到添加這些材料通常會降低氧化鋯的介電常數或者產生更大的漏電流。氧化鋯和氧化鉿有類似的化學結構，且能夠完全互溶。相較於氧化鉿，以二氧化鋯鉿當作閘極氧化層材料則擁有高電導，藉以降低電荷捕捉效應，獲得較高的驅動電流並改善N型金屬-氧化物-半導體的臨界電壓不穩的問題，以提升氧化值的品質和可靠度，如漏電流、磁滯、介面密度和優越的晶圓級厚度均勻性，在經過一連串的負壓測試，如溫度或大偏壓的情況下仍然能夠正常的運作。
Gate First製程在業界的發展比Gate Last製程早而且成熟，這使得Gate First製程有個好處，就是在積體電路設計和製程上不需改變太多步驟即可作業。但是對Gate First元件來說，不同程度的沉積會形成不同厚度的覆蓋層。這些沉積的覆蓋層可以改善漏電流的問題，但是越厚的覆蓋層會造成閘極介電層之中有更多的介面陷阱和氧空缺，進而造成更大的臨界電壓偏移。最大的關鍵在於，進入28奈米世代之後，Gate Last製程的元件電性將會比Gate First製程優良。
本論文主要在探討以原子層沈積法沈積高品質二氧化鋯鉿薄膜，藉由原子層沈積法的均勻性及高階梯覆蓋性，製作二氧化鋯鉿金氧半場效電晶體的閘極氧化層。此外，我們亦研究利用不同的氮化處理對於二氧化鋯鉿金氧半場效電晶體的等效氧化層厚度微縮能力的比較作討論。最後，我們研究以電漿氮化法(Decoupled Plasma Nitridation)不同製程參數調變時所處理的超薄氮化二氧化鋯鉿薄膜與元件的特性與均有深入的研究。論文第二章在ALD high-k薄膜製程中，比較使用不同種類的前導物(precursor)所製作的La2O3覆蓋層(capping layer)其材料物性特徵，與探討它們應用在nMOS的閘極優先型製程中，對於high-k介電閘極層MOS元件特性的影響。第三章研究ALD HfZrO2疊層中置入不同ZrO2位置的效應，並搭配La2O3覆蓋層在閘極優先或閘極後製的後續製程對於元件特性的比較。第四章研究ALD HfZrO2 介電層中的ZrO2 濃度效應與MOS元件可靠度的關係。第五章探討ALD HfZrO2經由氨氣熱氮化法(NH3 thermal nitridation)與去耦合電漿氮化(DPN)方式所製成的超薄氮化氧化鋯鉿(HfZrON)介電層的材料物性及其MOS元件等效氧化層厚度(EOT)縮微能力比較。第六章針對ALD HfZrO2的去耦合電漿氮化(DPN)製程，將電漿製程參數做最佳化調整，可有效地降低HfZrON的等效氧化層厚度，精確控制氮分佈測量圖，對於未來CMOS元件縮減厚度應用上具備絶佳的潛能。

In the downscaling process of the semiconductor industry , besides reduction in the horizontal direction, the basic operation that such proportions as the vertical direction must be done to reduce and maintain the properties of the component . Therefore , in 45 and 32 nm technology node , the thickness of the traditional insulator SiO2 will need to be reduced to about 1nm . However, the electrons of the gate can flow through gate oxide into drain by tunneling in this case, and produce large leakage current and thus the degradation of mobility . To decrease the leakage current, one must increase the physical thickness of the gate insulator to reduce the tunneling current, while keeping the EOT (equivalent oxide thickness) to maintain the characteristics of the devices. Using insulators with high dielectric constant is one of the attractive and popular method to research the problem. Among many candidate dielectric material, hafnium oxide (HfO2) has been extensively studied.
Hafnium oxide exhibits good thermodynamic stability on direct contact with Si , high dielectric constants, a large band offset with Si, suffers from mobility degradation, fixed charge and threshold voltage instability, etc.. The properties of HfO2 can be improved by adding different elements such as Si, Al, N, Ti ,Ta. It is reported that zirconium oxide (ZrO2) has similar chemical structure to that of HfO2 and is completely miscible in HfO2. HfZrO2 gate dielectric showed: higher trans-conductance. less charge trapping, higher drive current, lower NMOS Vt, reduced C-V hysteresis, lower interface state density, superior wafer-level thickness uniformity, and longer PBTI lifetime.
Gate first process was developed into manufacturing earlier than gate last. The fact leads to one of the advantages is that the integrated circuits design would not have to be changed so much for gate first. But for gate first devices, the various cycles of deposition would form various thicknesses of the capping layer. The deposition of capping layer could improve the leakage problems, but thicker capping layer of the gate first devices would induce more Dit and oxygen vacancies in gate dielectric. One important point is that the GL devices will have better characteristics than the GF ones while the fabrication process beyond 28nm technology node.
This research is to investigate the highly transparent HfZrO2 thin film used by Atomic Layer Deposition (ALD). Because of large area uniformity and high step coverage in fabricating MOSFET gate oxide application with the HfZrO2 films.。Besides, we study different nitridation treatment for the EOT scalability of ALD HfZrO2 MOSFETs application. Finally, we study the film and device characteristics of ALD HfZrON gate stack by tuning the process parameter of DPN as well. In the 2nd chapter, we studied the effects of the La2O3 capping layer interposed in Si/SiO2/HfO2/TiN high-k gate dielectric stacks prepared from two different ALD lanthanum precursors. In the chapter 3 and 4, we have systematically investigate hafnium zirconate (HfZrO2)/SiO2 MOSCAP device characteristics by changing the ZrO2 position and concentration in ALD HfO2 gate stack. In the chapter 5, NH3 thermal annealing and decoupled plasma nitridation (DPN) were employed for investigating the EOT scaling of HfZrO2. In the chapter 6, we compared the DPN and post nitridation anneal (PNA) processes for equivalent oxide thickness (EOT) scaling of ALD HfZrO2 gate dielectric. Finally, the Chapter 7 provides important conclusions and suggestion for future works worthy of further research.

Chapter-1 Reference

[1] R. H. Dennard, F. H. Gaensslen, H-N, Yu, V. L. Rideout, E. Bassous, and A. R. LeBlanc, "Design of ion-implanted MOSFET’s with very small physical dimensions," IEEE J. Solid-State Circuits, vol. SC-9, pp. 256-268, 1974
[2] International Technology Roadmap for Semiconductor (ITRS), 2009
[3] fttp://download.intel.com/technology/architecture-silicon/ISSCC_09_plenary_bohr_present ation.pdf
[4] S. M. Sze, and K. K. Ng, Physics of Semiconductor Devices 3rd Edition, John Wiley & Sons, Inc., 2007
[5] Y. Taur and T. Ning, Fundamentals of Modern VLSI Devices, Cambridge, 1998.
[6] IEDM 2010 Short Course: Reliability.
[7] T. Hattori, T .Yoshida, T. Shiraishi, K. Takahashi, H. Nohira, S. Joumori, K. Nakajima, M. Suzuki, K. Kimura, I. Kashiwagi, O. Oshima, S. Ohmi, and H. Iwai, “Composition, chemical structure, and electronic band structure of rare earth oxide/Si(100) interface transition layer,” Microelectronic Engineering, vol. 72, pp. 283-287, 2004.
[8] T. Ando, M. M. Frank, K. Choi, C. Choi, J. Bruley, M. Hopstaken, M. Copel, E. Cartier, A. Kerber, A. Callegari, D. Lacey, S. Brown, Q. Yang, and V. Narayanan, “Understanding Mobility Mechanisms in Extremely Scaled HfO2 (EOT 0.42 nm) Using Remote Interfacial Layer Scavenging Technique and Vt-tuning Dipoles with Gate-First Process,” IEDM Tech. Dig., pp.423-426, 2009.
[9] P. Ranade, T. Ghani, K. Kuhn , K. Mistry, S. Pae, L. Shifren, M. Stettler, K. Tone, S. Tyagi and M. Bohr, "High Performance 35nm LGATE CMOS Transistors Featuring NiSi Metal Gate (FUSI), Uniaxial Strained Silicon Channels and 1.2nm Gate Oxide," IEDM Tech. Dig., p. 217-220, 2005.
[10] L.-Å. Ragnarsson, Z. Li, J. Tseng, T. Schram, E. Rohr, M. J. Cho, T. Kauerauf, T. Conard, Y. Okuno, B. Parvais, P. Absil, S. Biesemans, and T. Y. Hoffmann, "Ultralow-EOT (5 Å) Gate-First and Gate-Last High Performance CMOS Achieved by Gate-Electrode Optimization," IEDM Tech. Dig., pp. 663-666, 2009.
[11] F. Arnaud, J. Liu, Y. M.Lee, K. Y.Lim, S. Kohler, J. Chen, B. K. Moon, C. W. Lai, M. Lipinski, L. Sang, F. Guarin, C. Hobbs, P. Ferreira, K. Ohuchi, J. Li, H. Zhuang, P. Mora, Q. Zhang, D. R. Nair, D. H. Lee, K. K. Chan, S. Satadru, S. Yang, J. Koshy, W. Hayter, M. Zaleski, D. V. Coolbaugh, H. W. Kim, Y. C. Ee, J. Sudijono, A. Thean, M. Sherony, S. Samavedam, M. Khare, C. Goldberg, and A. Steegen, "32nm General Purpose Bulk CMOS Technology for High Performance Applications at Low Voltage," IEDM Tech. Dig., pp. 633-636, 2008.
[12] T. Tomimatsu, Y. Goto, H. Kato, M. Amma, M. Igarashi, Y. Kusakabe, M. Takeuchi, S.Ohbayashi, S.Sakashita, T. Kawahara, M. Mizutani, M. Inoue, M. Sawada, Y. Kawasaki, S. Yamanari, Y. Miyagawa, Y. Takeshima, Y. Yamamoto, S. Endo, T. Hayashi, Y. Nishida, K. Horita, T. Yamashita, H. Oda, K. Tsukamoto, and Y. Inoue, "Cost-effective 28nm LSTP CMOS Using Gate-First Metal Gate/High-k Technology," VLSI Tech. Dig., pp. 36-37, 2009.
[13] H. R. Harris, P. Kalra, P. Majhi, M. Hussain, D. Kelly, J. Oh, D. He, C. Smith, J. Barnett, P. D. Kirsch, G. Gebara, J. Jur, D. Lichtenwalner, A. Lubow, T. P. Ma, G. Sung, S. Thompson, B. H. Lee, H.-H. Tseng and R. Jammy, "Band-engineered Low PMOS VT with High-k/Metal Gates Featured in a Dual Channel CMOS Integration Scheme," VLSI Tech. Dig., pp. 154-155, 2007.
[14] K. Mistry, C. Allen, C. Auth, B. Beattie, D. Bergstrom, M. Bost, M. Brazier, M. Buehler, A. Cappellani, R. Chau, C.-H. Choi, G. Ding, K. Fischer, T. Ghani, R. Grover, W. Han, D. Hanken, M. Hattendorf, J. He, J. Hicks , R. Huessner, D. Ingerly, P. Jain, R. James, L. Jong, S. Joshi, C. Kenyon, K. Kuhn, K. Lee, H. Liu, J. Maiz, B. McIntyre, P. Moon, J. Neirynck, S. Pae, C. Parker, D. Parsons, C. Prasad, L. Pipes, M. Prince, P. Ranade, T. Reynolds, J. Sandford, L. Shifren, J. Sebastian, J. Seiple, D. Simon, S. Sivakumar, P. Smith, C. Thomas, T. Troeger, P. Vandervoorn, S. Williams, and K. Zawadzki, “A 45nm Logic Technology with High-k+Metal Gate Transistors, Strained Silicon, 9 Cu Interconnect Layers, 193nm Dry Patterning, and 100% Pb-free Packaging,” IEDM Tech. Dig., pp. 247–250, 2007
[15] K. Choi, H. Jagannathan, C. Choi, L. Edge, T. Ando, M. Frank, P. Jamison, M. Wang, E. Cartier, S. Zafar, J. Bruley, A. Kerber, B. Linder, A. Callegari, Q. Yang, S. Brown, J. Stathis, J. Iacoponi, V. Paruchuri, and V. Narayanan, "Extremely Scaled Gate-First High-k/Metal Gate Stack with EOT of 0.55nm Using Novel Interfacial Layer Scavenging Techniques for 22nm Technology Node and Beyond," VLSI Tech. Dig., pp. 138-139, 2009.
[16] C. M. Lai, C. T. Lin, L. W. Cheng, C. H. Hsu, J. T. Tseng, T. F. Chiang, C. H. Chou, Y. W. Chen, C. H. Yu, S. H. Hsu, C. G. Chen, Z. C. Lee, J. F. Lin, C. L. Yang, G. H. Ma, and S. C. Chien, "A Novel Hybrid High-k/Metal Gate Process for 28nm High Performance CMOSFETs," IEDM Tech. Dig., pp. 655-658, 2009.
[17] C. Auth, A. Cappellani, J.-S. Chun, A. Dalis, A. Davis, T. Ghani, G. Glass, T. Glassman, M. Harper, M. Hattendorf, P. Hentges, S. Jaloviar, S. Joshi, J. Klaus, K. Kuhn, D. Lavric, M. Lu, H. Mariappan, K. Mistry, B. Norris, N. Rahhal-orabi, P. Ranade, J. Sandford, L. Shifren%, V. Souw, K. Tone, F. Tambwe, A. Thompson, D. Towner, T. Troeger, P. Vandervoorn, C. Wallace, J. Wiedemer, and C. Wiegand, "45nm High-k + Metal Gate Strain-enhanced Transistors," VLSI Tech. Dig., pp. 128-129, 2008.
[18] M. V. Fischetti. D. A. Neumayer and E. A. Cartier, J. Appl. Phys. 90,4587 (2001).
[19] J. H. Stathis and D. J. DiMaria, Tech. Dig. IEDM’98, 167 (1998).
[20] R. Degraeve, B. Kaczer and G. Groeseneken, Semicond. Sci. Technol. 15,436 (2000).
[21] B. E. Weir, M. A. Alam, J. D. Bude, P. J. Siverman, A. Ghetti, F. Baumann, P. Diodato, D. Monroe, T. Sorsch, G L. Timp, Y. Ma, M. M. Brown, A. Hamad, D. Hwang and P. Mason, Semicond. Sci. Technol. 15,455 (2000).
[22] M. L. Green, E. P. Gusev, R. Degraeve and E. L. Garfunkel, J. Appl. Phys. 90,2057 (2001).
[23] M. Hirose, M. Koh, W. Mizubayashi, H. Murakami, K. Shibahara and S. Miyazaki, Semicond. Sci. Technol. 15,485 (2000).
[24] A. I. Kingon, J. P. Maria and S. K. Streiffer, Nature 406, 1032 (2000).
[25] G. D. Wilk, R. M. Wallace and J. M. Anthony, J. Appl. Phys. 89,5243, (2001).
[26] H. Watanabe, Appl. Phys. Lett. 78, 3803 (2001).
[27] R. J. Carter, E. Cartier, M. Caymax, S. De. Gendt, R. Degraeve, G. Groeseneken, M. Heyns, T. Kauerauf, A. Kerber, S. Kubicek, G Lujan, L. Pantisano, W. Tsai, E. Young, Ext. Abst. IWGI2000, 95 (2000) (Tokyo).
[28] N. Kimizuka, K. Yamaguchi, K. Imai, T. Iizuka, C. T. Liu, R. C. Keller and T. Horiuchi, Dig. Symp. VLSI Technology, 92 (2000) (Hawaii).
[29] G. Lucovsky, Y. Wu, H. Niimi, V. Misra, and J. C. Phillips, J. Vac. Sci. Technol. 817, 1806 (1999).
[30] K. P. Cheung, Proc. 6th ISSICT, 315 (2001), (Shanghai).
[31] E. P. Gusev, E. Cartier, D. A. Buchanan, M. Gribelyuk, and M. Copel., AVS Topical Conf. on Atomic Layer Deposition, May 14, 2001
[32] M. Ritala and M. Leskela, “ Atomic Layer Deposition,” Handbook of Thin Film Materials, H. S. Nalwa ed., Academic Press, 2001, Vol.1, Chap. 2
[33] D. H. Triyoso, R. I. Hegde, B. E. White, and P. J. Tobin , "Physical and Electrical Characteristics of Atomic-Layer-Deposited Hafnium Oxide Formed Using Hafnium Tetrachloride and Tetrakis(ethylmethylaminohafnium)," Jour. of Appl. Physics, vol. 97, 124107, pp. 1-9, 2005.
[34] L. Niinistö, M. Nieminen, J. Päiväsaari, J. Niinistö, M. Putkonen, M. Nieminen, "Advanced Electronic and Optoelectronic Materials by Atomic Layer Deposition: An Overview with Special Emphasis on Recent Progress in Processing of High-k Dielectrics and Other Oxide Materials," Physica Status Solidi (a), 201, p. 1443–1452, 2004.

Chapter-2 Reference

[1] D. H. Triyoso, R. I. Hegde, J. Grant, P. Fejes, R. Liu, D. Roan, M. Ramon, D. Werho, R. Rai, L. B. La, J. Baker, C. Garza, T. Guenther, B. E. White, Jr., and P. J. Tobin, “Film properties of ALD HfO2 and La2O3 gate dielectrics grown on Si with various pre-deposition treatments,” J. Vac. Sci. Technol. B, vol.22, pp.2121-2127, 2004.
[2] S. Harasek, H. D. Wanzenboeck, and E. Bertagnolli, “Compositional and electrical properties of zirconium dioxide thin films chemically deposited on silicon,” J. Vac. Sci. Technol., A, vol. 21, pp. 653–659, 2003.
[3] H. Wang, J. J. Wang, R. Gordon, J. M. Lehn, H. Li, D. Hong, and D. V. Shenai, “Atomic Layer Deposition of Lanthanum-Based Ternary Oxides,” Electrochem. Solid-State Lett., vol.12, no.4, pp.G13-G15, 2009.
[4] S. Guha, E.P. Gusev, M. Copel, L-Å. Ragnarsson, and D.A. Buchanan, "Compatibility challenges for high-k materials integration into CMOS technology", MRS Bull., vol. 27, pp. 226-229, 2002.
[5] R. M. C. de Almeida and I. J. R. Baumvol, “Reaction-diffusion in high-κ dielectrics on Si,” Surf. Sci. Rep., vol. 49, p.1, 2003.
[6] M. V. Fischetti, D. A. Neumayer, and E. A. Cartier, “Effective electron mobility in Si inversion layers in metal-oxide-semiconductor systems with a high-k insulator: The role of remote phonon scattering,” J. Appl. Phys., vol. 90, no. 9, pp. 4587–4608, 2001.
[7] M. A. Quevedo-Lopez, S. A. Krishnan, P. D. Kirsch, G. Pant, B. E. Gnade, and R. M. Wallace, “Ultrascaled hafnium silicon oxynitride gate dielectrics with excellent carrier mobility and reliability,” Appl. Phys. Lett., vol. 87, no. 26, p. 262 902, Dec. 2005.
[8] P. D. Kirsch, M. A. Quevedo-Lopez, H.-J. Li, Y. Senzaki, J. J. Peterson, S. C. Song, S. A. Krishnan, N. Moumen, J. Barnett, G. Bersuker, P. Y. Hung, B. H. Lee, T. Lafford, Q. Wang, D. Gay, and J. G. Ekerdt, “Nucleation and growth study of atomic layer deposited HfO2 gate dielectrics resulting in improved scaling and electron mobility,” J. Appl. Phys., vol. 99, no. 2, p. 023 508, Jan. 2006.
[9] L.-A. Ragnarsson, S. Severi, L. Trojman, K. D. Johnson, D. P. Brunco, M. Aoulaiche, M. Houssa, T. Kauerauf, R. Degraevere, A. Delabie, V. S. Kaushik, S. D. Gendt, W. Tsai, G. Groeseneken, K. D. Meyer, and M. Heyns “Electrical Characteristics of 8-Å EOT HfO2/TaN Low Thermal-Budget n-Channel FETs With Solid-Phase Epitaxially Regrown Junctions,” IEEE Trans. Electron Devices, vol. 53, no. 7, pp. 1657-1668, July 2006.
[10] B. Onsia, T. Conard, S. De Gendt, H. M. F. De Smedt, A. Delabie, C. Gottschalk, M. Green, M. Heyns, S. Lin, P. Mertens, W. Tsai, and C. Vinckier, “On the application of a thin ozone based wet chemical oxide as an interface for ALD high-κ deposition,” Solid State Phenom., vol. 103/104, pp. 19–22, 2005.
[11] M. L. Green, A. J. Allen, X. Li, J. Wang, J. Ilavsky, A. Delabie, R. L. Puurunen, and B. Brijs, “Nucleation of atomic-layer-deposited HfO2 films, and evolution of their microstructure, studied by grazing incidence small angle x-ray scattering using synchrotron radiation,” Appl. Phys. Lett., vol. 88, 032907, pp. 1-3, 2006.
[12] Z. M. Rittersma, F. Roozeboom, M. A. Verheijen, J. G. M. van Berkum, T. Dao, J. H. M. Snijders, E. Vainonen-Ahlgren, E. Tois, M. Tuominen, and S. Haukka, “HfSiO4 dielectric layers deposited by ALD using HfCl4 and NH2(CH2)3Si(OC2H5)3 precursors,” J. Electrochem. Soc. vol. 151, pp. C716, 2004.
[13] Y. Senzaki, S. Park, H. Chatham, L. Bartholomew, and W. Nieveen, ”Atomic layer deposition of hafnium oxide and hafnium silicate thin films using liquid precursors and ozone,” J. Vac. Sci. Technol. A, vol. 22, pp. 1175-1181, 2004.
[14] S. Kamiyama, T. Miura, and Y. Nara, “Impact of O3 Concentration on Ultrathin HfO2 Films Deposited on HF-Cleaned Silicon Using Atomic Layer Deposition with Hf[N(CH3)(C2H5)]4, “ Electrochem. Solid-State Lett., vol. 9, no. 6, pp. G285-G288, 2006.
[15] K. Kukli, M. RitaLa, T. Sajavaara, J. Keinonen, and M. Leskelä, “Comparison of hafnium oxide films grown by atomic Layer deposition from iodide and chloride precursors”, Chem. Vap. Deposition vol. 8, pp. 199, 2002.
[16] X. Lui, S. Ramanathan, A. Longdergan, A. Srivastava, E. Lee, T. E. Seidel, J. T. Barton, D. Pang, and R. G. Gordon, ” ALD of Hafnium Oxide Thin Films from Tetrakis-(ethylmethylamino)hafnium and Ozone, ” J. Electrochem. Soc., vol. 152, pp. G213-G219, 2005.
[17] L.-Å. Ragnarsson, S. Severi, L. Trojman, D. P. Brunco, K. D. Johnson, A. Delabie, T. Schram, W. Tsai, G. Groeseneken, K. De Meyer, S. De Gendt, and M. Heyns, “High Performing 8 Å EOT HfO2 / TaN Low Thermal-Budget n-channel FETs with Solid-Phase Epitaxially Regrown (SPER) Junctions,” in Proc. Symp. VLSI Tech., 2005, pp. 234–235.
[18] E. Cartier, F. R. McFeely, V. Narayanan, P. Jamison, B. P. Inder, M. Copel, V. K. Paruchuri, V. Basker, R. Haight, D. Lim, R. Carruthers, T. Shaw, M. Steen, J. Sleight, J. Rubino, H. Deligianni, S. Guha, R. Jammy, and G. Shahidi, “Role of Oxygen Vacancies in VFB/Vt stability of pFET metals on HfO2,” in Proc. Symp. VLSI Tech., 2005, pp. 230–231.
[19] C. C. Hobbs, L. R. C. Fonseca, A. Knizhnik, V. Dhandapani, S. B. Samavedam, W. J. Taylor, J. M. Grant, L. G. Dip, D. H. Triyoso, R. S. Rai, E. A. Hebert, H. H. Tseng, S. G. H. Anderson, B. E. White, and P. J. Tobin, “Fermi-Level Pinning at the Polysilicon/Metal–Oxide Interface—Part II,” IEEE Trans. Electron Devices, vol. 51, no. 6, pp. 978-984, Jun. 2004.
[20] E. Miranda, J. Molina, Y. Kim, and H. Iwai, “Effects of high-field electrical stress on the conduction properties of ultrathin La2O3 films, “ Appl. Phys. Lett., vol. 86 , 232104, pp. 1-3, 2005.
[21] S. Guha, E. Cartier, M.A. Gribelyuk, N.A. Bojarczuk, and M.C. Copel, “Atomic beam deposition of lanthanum- and yttrium-based oxide thin films for gate dielectrics,” Appl. Phys. Lett., vol. 77, no. 17, pp. 2710-2712, Oct. 2000.
[22] H.Yamada, T.Shimizu, A.Kurokawa, K.Ishii, and E.Suzuki, "MOCVD of High-Dielectric-Constant Lanthanum Oxide Thin Films", J. Electrochem. Soc., vol. 150, no. 8, pp. G429-G435, Aug. 2003.
[23] M. Suzuki, T. Yamaguchi, N. Fukushima, and M. Koyama,” LaAlO3 gate dielectric with ultrathin equivalent oxide thickness and ultralow leakage current directly deposited on Si substrate,” J. Appl. Phys. vol. 103, no. 3, 034118, pp. 1-5, 2008._
[24] K. Kukli, M. Ritala, V. Pore, M. Leskelä, T. Sajavaara, R. I. Hedge, D. C. Gilmer, P. J. Tobin, A. C. Jones, and H. C. Aspinall,, “ Atomic Layer Deposition and Properties of Lanthanum Oxide and Lanthanum Aluminum Oxide Films, Chem. Vap. Deposition vol.12, pp. 158–164, 2006.
[25] L.Å. Ragnarsson,V. S. Chang, H. Y. Yu, H. J. Cho, T. Conard, K. M. Yin, A. Delabie, J. Swerts, T. Schram, S. D. Gendt, and S. Biesemans, “Achieving Conduction Band-Edge Effective Work Functions by La2O3 Capping of Hafnium Silicates,” IEEE Electron Device Lett., vol. 28, no. 6, pp. 486-488, June 2007.
[26] M. Ritala, and J. Niinistö, in Chemical Vapour Deposition: Precursors, Processes and Applications, ed. A. C. Jones and M. L. Hitchman, Royal Society of Chemistry, chapter 4, pp. 158, 2009.
[27] J. Swerts, N. Peys, L. Nyns, A. Delabie, A. Franquet, J. W. Maes, S. V. Elshocht, and S. D. Gendta, “Impact of Precursor Chemistry and Process Conditions on the Scalability of ALD HfO2 Gate Dielectrics,” J. Electrochem. Soc., vol. 157, pp. G26-G31, 2010.
[28] A. Delabie, M. Caymax, B. Brijs, D. P. Brunco, T. Conard, E. Sleeckx, S. van Elshocht, L.-Å. Ragnarsson, S. De Gendt, and M. Heyns, “Scaling to sub-1 nm equivalent oxide thickness with hafnium oxide deposited by atomic layer deposition,” J. Electrochem. Soc., vol. 153, no. 8, pp. F180–F187, 2006.
[29] D. Triyoso, R. Liu, D. Roan, M. Ramon, N. V. Edwards, R. Gregory, D. Werho, J. Kulik, G. Tam, E. Irwin, X.-D. Wang, L. B. La, C. Hobbs, R. Garcia, J. Baker, B. E. White, Jr., and P. Tobin, “Impact of deposition and annealing temperature on material and electrical characteristics of ALD HfO2,” J. Electrochem. Soc., vol. 151, no. 10, pp. F220–F227, 2004.
[30] E. P. Gusev, C. Cabral, M. Copel, C. Emic, M. Gribelyuk, “Ultrathin HfO2 film grown on silicon by atomic layer deposition for advanced gate dielectrics applications,” in Microelectronic Engineering, vol. 69 , pp. 145-151, 2003.
[31] M. M. Frank, Y. J. Chabal, M. L. Green, A. Delabie, B. Brijs, G. D. Wilk, M.-Y. Ho, E. B. O. da Rosa, I. J. R. Baumvol, and F. C. Stedile, “Enhanced initial growth of atomic-layer-deposited metal oxides on hydrogen-terminated silicon,” Appl. Phys. Lett., vol. 83, no. 4, pp. 740-742, July 2003.
[32] M. Cho, R. Degraeve, G. Pourtois, A. Delabie, L. A. Ragnarsson, T. Kauerauf, G. Groeseneken, S. De Gendt, M. M. Heyns, and C. S. Hwang,” Study of the Reliability Impact of Chlorine Precursor Residues in Thin Atomic-Layer-Deposited HfO2 Layers,” IEEE Trans. Electron Devices, vol. 54, no. 4, pp. 752-758, Apr. 2007.
[33] J. J. Peterson, C. D. Young, J. Barnett, S. Gopalan, J. Gutt, C.-H. Lee, H.-J. Li, T.-H. Hou, Y. Kim, C. Lim, N. Chaudhary, N. Moumen, B.-H. Lee, G. Bersuker, G. A. Brown, P. M. Zeitzoff, M. I. Gardner, R. W. Murto, and H. R. Huff, “Subnanometer scaling of HfO2 /metal electrode gate stacks,” Electrochem. Solid-State Lett., vol. 7, no. 8, pp. G164–G167, 2004.
[34] Available from: <http://www.rohmhaas.com>.
[35] M. Nieminen, M. Putkonen, and L. Niinistö, “Formation and stability of lanthanum oxide thin films deposited from B-diketonate precursor,” Applied Surface Science, vol. 174, no. 2, pp. 155-165, Apr. 2001.
[36] J. Niinistö, M. Putkonen, L. Niinistö, K. Arstila, T. Sajavaara, J. Lu, K. Kukli, M. Ritala, M. Leskelä, ” HfO2 Films Grown by ALD Using Cyclopentadienyl-Type Precursors and H2O or O3 as Oxygen Source,” J. Electrochem. Soc. vol. 153, pp. F39-F45, 2006.
[37] H. N. Alshareef, M. Quevedo-Lopez, H. C. Wen, R. Harris, P. Kirsch, P. Majhi, B. H. Lee, and R. Jammy, " Work function engineering using lanthanum oxide interfacial layers," Appl. Phys. Lett. vol. 89, 232103, pp. 1-3, 2006.
[38] S. Guha, V. K. Paruchuri, M. Copel, V. Narayanan, Y. Y. Wang, P. E. Batson, N. A. Bojarczuk, B. Linder, and B. Doris, “Examination of flatband and threshold voltage tuning of HfO2 /TiN field effect transistors by dielectric cap layers,“ Appl. Phys. Lett. vol. 90, 092902, pp. 1-3, 2007.
[39] C. H. An, M. S. Lee, J. Y. Choi, and H. Kim, "Change of the trap energy levels of the atomic layer deposited HfLaOx films with different La concentration," Appl. Phys. Lett. vol. 94, 262901, pp. 1-3, 2009.

Chapter-3 Reference

[1] P. Sivasubramani, T. S. Böscke, J. Huang, C. D.Young, P. D. Kirsch, S. A. Krishnan, M. A. Quevedo-Lopez, S. Govindarajan, B. S. Ju, H. R. Harris, D. J. Lichtenwalner, J. S. Jur, A. I. Kingon, J. Kim, B. E. Gnade, R. M. Wallace, G. Bersuker, B. H. Lee, and R. Jammy, ” Dipole Moment Model Explaining nFET Vt Tuning Utilizing La, Sc, Er, and Sr Doped HfSiON Dielectrics,” in Proc. Symp. VLSI Tech., 2007, pp. 68–69.
[2] I. P. Studenyak, M. Kranjcˇec, O. T. Nahusko, and O. M. Borets, “ Influence of Hf→Zr substitution on optical and refractometric parameters of Hf1−xZrxO2 thin films,” Thin Solid Films vol. 476, pp. 137-141, 2005.
[3] J. K. Schaeffer, L. R. C. Fonseca, S. B. Samavedam, Y. Liang, P. J. Tobin and B. E. White, “Contributions to the effective work function of platinum on hafnium dioxide,” Appl. Phys. Lett. vol. 85, pp. 1826-1828 , 2004.
[4] E. Cartier, F. R. McFeely, V. Narayanan, P. Jamison, B. P. Inder, M. Copel, V. K. Paruchuri, V. Basker, R. Haight, D. Lim, R. Carruthers, T. Shaw, M. Steen, J. Sleight, J. Rubino, H. Deligianni, S. Guha, R. Jammy, and G. Shahidi, “Role of Oxygen Vacancies in VFB/Vt stability of pFET metals on HfO2,” in Proc. Symp. VLSI Tech., 2005, pp. 230–231
[5] S. Guha, E. Cartier, M. A. Gribelyuk, N. A. Bojarczuk, and M. C. Copel, “Atomic beam deposition of lanthanum- and yttrium-based oxide thin films for gate dielectrics,” Appl. Phys. Lett. vol. 77, no.17, pp. 2710-2712, 2000.
[6] V. Narayanan, V. K. Paruchuri, N. A. Bojarczuk, B. P. Linder, B.Doris, Y. H. Kim, S. Zafar, J. Stathis, S. Brown, J.Arnold, , M. Copel, M. Steen, E. Cartier, A. Callegari, P. Jamison, J. -P. Locquet, D. L. Lacey, Y. Wang, P. E. Batson, P. Ronsheim, R. Jammy, M. P. Chudzik, M. Ieong, S. Guha, G. Shahidi, and T. C. Chen, “Band-Edge High-Performance High-κ /Metal Gate n-MOSFETs using Cap Layers Containing Group IIA and IIIB Elements with Gate-First Processing for 45 nm and Beyond,” in Proc. Symp. VLSI Tech., 2006, pp. 178-179.
[7] X. P. Wang, M. F. Li, C. Ren, X. F. Yu, C. Shen, H. H. Ma, A. Chin, C. X. Zhu, J. Ning, M. B. Yu, and D. L. Kwong, “Tuning Effective Metal Gate Work Function by a
[8] Novel Gate Dielectric HfLaO for nMOSFETs,“ IEEE Electron Device Lett. vol. 27, no. 1, pp. 31-33, Jan. 2006.
[9] H. N. Alshareef, M. Quevedo-Lopez, H. C. Wen, R. Harris, P. Kirsch, P. Majhi, B. H. Lee, R. Jammy, D. J. Lichtenwalner, J. S. Jur, and A. I. Kingon, “ Work function engineering using lanthanum oxide interfacial layers,“ Appl. Phys. Lett. vol. 89, 232103, pp. 1-3, 2006.
[10] S. Guha, V. K. Paruchuri, M. Copel, V. Narayanan, Y. Y. Wang, P. E. Batson, N. A. Bojarczuk, B. Linder, and B. Doris, “Examination of flatband and threshold voltage tuning of HfO2 /TiN field effect transistors by dielectric cap layers,“ Appl. Phys. Lett. vol. 90, 092902, pp. 1-3, 2007.
[11] M. Suzuki, T. Yamaguchi, N. Fukushima, and M. Koyama,” LaAlO3 gate dielectric with ultrathin equivalent oxide thickness and ultralow leakage current directly deposited on Si substrate,” J. Appl. Phys. vol. 103, no. 3, 034118, pp. 1-5, 2008.
[12] S. Guha, E. Cartier, M.A. Gribelyuk, N.A. Bojarczuk, and M.C. Copel, “Atomic beam deposition of lanthanum- and yttrium-based oxide thin films for gate dielectrics,“ Appl. Phys. Lett., vol. 77, no. 17, pp. 2710-2712, Oct. 2000.
[13] E. Miranda, J. Molina, Y. Kim, and H. Iwai, "MOCVD of High-Dielectric-Constant Lanthanum Oxide Thin Films," Appl. Phys. Lett. vol.86, 232104, pp.1-3, 2005.
[14] H.Yamada, T.Shimizu, A.Kurokawa, K.Ishii, and E.Suzuki, "MOCVD of High-Dielectric-Constant Lanthanum Oxide Thin Films", J. Electrochem. Soc., vol. 150, no. 8, pp. G429-G435, Aug. 2003.
[15] K. Kukli, M. Ritala, V. Pore, M. Leskela¨, T. Sajavaara, R. I. Hedge, D. C. Gilmer, P. J. Tobin, A. C. Jones, and H. C. Aspinall, “ Atomic Layer Deposition and Properties of Lanthanum Oxide and Lanthanum Aluminum Oxide Films, Chem. Vap. Deposition vol. 12, pp. 158–164, 2006.
[16] D. H. Triyoso, R. I. Hegde, J. K. Schaeffer, R. Gregory, X.-D. Wang, M. Canonico, D. Roan, E. A. Hebert, K. Kim, J. Jiang, R. Rai, V. Kaushik, and S. B. Samavedam, “Characteristics of atomic-layer-deposited thin HfxZr1−xO2 gate dielectrics,” J. Vac. Sci. Technol. B, Microelectron. Process. Phenom., vol. 25, no. 3, pp. 845–852, May/Jun. 2007.
[17] R. I. Hegde, D. H. Triyoso, P. J. Tobin, S. Kalpat, M. E. Ramon, H.-H. Tseng, J. K. Schaeffer, E. Luckowski, W. J. Taylor, C. C. Capasso, D. C. Gilmer, M. Moosa, A. Haggag, M. Raymond, D. Roan, J. Nguyen, L. B. La, E. Hebert, R. Cotton, X. D. Wang, S. Zollner, R. Gregory, D. Werho, R. S. Rai, L. Fonseca, M. Stoker, C. Tracy, B. W. Chan, Y. H. Chiu, and B. E. White Jr. “Microstructure Modified HfO2 Using Zr Addition with TaxCy Gate for Improved Device Performance and Reliability “, IEDM Tech. Dig., 2005, pp. 35-38.
[18] D. Y. Cho, H. S. Jung, and C. S. Hwang, “Structural properties and electronic structure of HfO2-ZrO2 composite films,” Phys. Rev. B vol. 82, pp. 094104-094110, 2010.

Chapter-4 Reference

[1] R. Chau, S. Datta, M. Doczy, B. Doyle, J. Kavalieros and M. Metz, "High-K/Metal-Gate Stack and Its MOSFET Characteristics," IEEE Electron Device Lett., vol. 25, no. 6, pp. 408-410, June 2004.
[2] R. I. Hegde, C. C. Hobbs, L. Dip, J. K. Schaeffer, and P. J. Tobin, "Impact of metal-oxide gate dielectric on minority carrier lifetime in silicon," Appl. Phys. Lett. vol. 80, no. 20, pp. 3850-3852, May 2002.
[3] G. D. Wilk, R. M. Wallace and J. M. Anthony, “Hafnium and zirconium silicates for advanced gate dielectrics,” J. Appl. Phys. vol. 87, pp. 484-492, 2000.
[4] M. L. Green, T. W. Sorsch, G. L. Timp, D. A. Muller, B. E. Weir, P. J. Silverman, S. V. Moccio, and Y. O. Kim, “Understanding the limits of ultrathin SiO2 and Si- ON gate dielectrics for sub-50 nm CMOS,” Microelectron. Eng. vol. 48, pp. 25-30, 1999.
[5] L. Manchanda, M. L. Green, R. B. van Dover, M. D. Morris, A. Kerber, Y. Hu, J.-P. Han, P. J. Silverman, T. W. Sorsch, G. Weber, V. Donnelly, K. Pelhos, F. Klemens, N. A. Ciampa, A. Kornblit, Y. O. Kim, J. E. Bower, D. Barr, E. Ferry, I. Jacobson, J. Eng, B. Busch and H. Schulte, “Si-Doped Aluminates for High Temperature Metal-Gate CMOS: Zr-Al-Si-O, A Novel Gate Dielectric for Low Power Applications, “, in IEDM Tech. Dig., 2000, pp. 23-26.
[6] R. Ludeke, M. T. Cuberes, and E. Cartier “Local transport and trapping issues in Al2O3 gate oxide structures,” Appl. Phys. Lett., vol. 76, pp. 2886-2888, 2000.
[7] I. P. Studenyak, M. Kranjcˇec, O. T. Nahusko, and O. M. Borets, “ Influence of Hf→Zr substitution on optical and refractometric parameters of Hf1−xZrxO2 thin films,” Thin Solid Films vol. 476, pp. 137-141, 2005.
[8] J. K. Schaeffer, L. R. C. Fonseca, S. B. Samavedam, Y. Liang, P. J. Tobin and B. E. White, “Contributions to the effective work function of platinum on hafnium dioxide,” Appl. Phys. Lett. vol. 85, pp. 1826-1828 , 2004.
[9] E. Cartier, F. R. McFeely, V. Narayanan, P. Jamison, B. P. Inder, M. Copel, V. K. Paruchuri, V. Basker, R. Haight, D. Lim, R. Carruthers, T. Shaw, M. Steen, J. Sleight, J. Rubino, H. Deligianni, S. Guha, R. Jammy, and G. Shahidi, “Role of Oxygen Vacancies in VFB/Vt stability of pFET metals on HfO2,” in Proc. Symp. VLSI Tech., 2005, pp. 230–231.
[10] D. H. Triyoso, R. I. Hegde, J. K. Schaeffer, R. Gregory, X.-D. Wang, M. Canonico, D. Roan, E. A. Hebert, K. Kim, J. Jiang, R. Rai, V. Kaushik, and S. B. Samavedam, “Characteristics of atomic-layer-deposited thin HfxZr1−xO2 gate dielectrics,” J. Vac. Sci. Technol. B, Microelectron. Process. Phenom., vol. 25, no. 3, pp. 845–852, May/Jun. 2007.
[11] R. I. Hegde, D. H. Triyoso, S. B. Samavedam, and B. E. White, Jr., “Hafnium zirconate gate dielectric for advanced gate stack applications,” J. Appl. Phys., vol. 101, no. 7, pp. 0741131–0741137, Apr. 2007.
[12] X. Zhao, D. Ceresoli, and D. Vanderbilt, " Structural, electronic, and dielectric properties of amorphous ZrO2 from ab initio molecular dynamics," Phys. Rev. B vol. 71, pp. 085107-085116, 2005.
[13] R. I. Hegde, D. H. Triyoso, P. J. Tobin, S. Kalpat, M. E. Ramon, H.-H. Tseng, J. K. Schaeffer, E. Luckowski, W. J. Taylor, C. C. Capasso, D. C. Gilmer, M. Moosa, A. Haggag, M. Raymond, D. Roan, J. Nguyen, L. B. La, E. Hebert, R. Cotton, X. D. Wang, S. Zollner, R. Gregory, D. Werho, R. S. Rai, L. Fonseca, M. Stoker, C. Tracy, B. W. Chan, Y. H. Chiu, and B. E. White Jr. “Microstructure Modified HfO2 Using Zr Addition with TaxCy Gate for Improved Device Performance and Reliability “, IEDM Tech. Dig., 2005, p. 35-38.
[14] D. H. Triyoso and R. I. Hegde, “Impact of Zr addition on properties of atomic layer deposited HfO2,” Appl. Phys. Lett., vol. 88, pp. 222901-222903, 2006.
[15] M. Suzuki, T. Yamaguchi, N. Fukushima, and M. Koyama , “LaAlO3 gate dielectric with ultrathin equivalent oxide thickness and ultralow leakage current directly deposited on Si substrate,” J. Appl. Phys., vol. 103, no.3, pp. 34118–34122, 2008.
[16] E. Miranda, J. Molina, Y. Kim, and H. Iwai, “Effects of high-field electrical stress on the conduction properties of ultrathin La2O3 films,” Appl. Phys. Lett., vol. 86, pp. 232104-232106, 2005.
[17] H.Yamada, T.Shimizu, A.Kurokawa, K.Ishii, and E.Suzuki, "MOCVD of High-Dielectric-Constant Lanthanum Oxide Thin Films", J. Electrochem. Soc., vol. 150, no. 8, pp. G429-G435, Aug. 2003.
[18] K. Kukli, M. Ritala, V. Pore, M. Leskela¨, T. Sajavaara, R. I. Hedge, D. C. Gilmer, P. J. Tobin, A. C. Jones, and H. C. Aspinall, “ Atomic Layer Deposition and Properties of Lanthanum Oxide and Lanthanum Aluminum Oxide Films, Chem. Vap. Deposition vol.12, pp. 158–164, 2006.
[19] C. K. Chiang, C. H. Wu, H. Y. Huang, J. F. Lin, C. L. Yang, J. Y. Wu, and S. J. Wang: Ext. Abstr. Solid State Devices and Materials, 2011, pp. 1.
[20] J. L. Gavartin, L. Fonseca, G. Bersuker, and A. L. Shluger, “Ab initio modeling of structure and defects at the HfO2/Si interface,” Microelectron. Eng., vol. 80, no. 17, pp. 412–415, Jun. 2005.
[21] S. G. Lim, S. Kriventsov, T. N. Jackson, J. H. Haeni, D. G. Schlom, A. M. Balbashov, R. Uecker, P. Reiche, J. L. Freeout, and G. Lucovsky , “Dielectric functions and optical bandgaps of high-K dielectrics for metal-oxide-semiconductor field-effect transistors by far ultraviolet spectroscopic ellipsometry,” J. Appl. Phys., vol. 91, no. 7, pp. 4500-4505, Apr. 2002.
[22] V. V. Afanas’ev, M. Houssa, A. Stesman, and M. M. Heins, “Band alignments in metal–oxide–silicon structures with atomic-layer deposited Al2O3 and ZrO2,” J. Appl. Phys., vol. 91, no. 5, pp. 3079-3084, Mar. 2002.
[23] S. Miyazaki, M. Narasaki, M. Ogasawara, and M. Hirose , “Chemical and electronic structure of ultrathin zirconium oxide films on silicon as determined by photoelectron spectroscopy,” Solid-State Electron. vol. 16, pp. 1679-1685, 2002.
[24] N. Ikarashi and K. Manabe, “Spatially-resolved valence-electron energy-loss spectroscopy of Zr-oxide and Zr-silicate films,” Appl. Phys. Lett., vol. 80, no. 22, pp. 4127-4129, June 2002.
[25] V. V. Afanas’ev , A. Stesmans, and W. Tsai, “Determination of interface energy band diagram between (100) Si and mixed Al–Hf oxides using internal electron photoemission,” Appl. Phys. Lett., vol. 82, no. 2, pp. 245-247, Jan. 2003.
[26] J. Robertson, " Band offsets of wide-band-gap oxides and implantation for future electronic devices, " J. Vac. Sci. Technol. B, Microelectron. Process. Phenom., vol. 18, pp. 1785, 2000.
[27] M. Houssa, V. V. Afanas’ev, A. Stesmans, and M. M. Heynes, “Variation in the fixed charge density of SiOx /ZrO2 gate dielectric stacks during postdeposition oxidation,” Appl. Phys. Lett., vol. 77, no. 12, pp. 1885-1887, Sep. 2000.
[28] D. H. Triyoso, R. I. Hegde, J. K. Schaeffer, D. Roan, P. J. Tobin, S. B. Samavedam, B. E. White, Jr., R. Gregory, and X.-D. Wang, “Impact of Zr addition on properties of atomic layer deposited HfO2,” Appl. Phys. Lett., vol. 88, pp. 222901-222903, 2006.
[29] J. C. Liao, Y. K. Fang, Y. T. Hou, W. H. Tseng, C. I. Yang, P. F. Hsu, Y. S. Chao, K. C. Lin, K. T. Huang, T. L. Lee, and M. S. Liang,” Observation of Reliability of HfZrOX Gate Dielectric Devices with Different Zr/Hf Ratios,” Jpn. J. Appl. Phys. vol. 47, pp. 2616-2620, 2008.

Chapter-5 Reference

[1] D. J. Frank, Y. Taur, and H. S. P. Wong , “Generalized Scale Length for Two-Dimensional Effects in MOSFET’s,” IEEE Electron Device Lett., vol. 19, pp. 385–387, 1998.
[2] S. Harasek, H. D. Wanzenboeck, E. Bertagnolli, “Compositional and electrical properties of zirconium dioxide thin films chemically deposited on silicon,” J. Vac. Sci. Technol. A, vol. 21, pp. 653, 2003.
[3] Y. T. Hou , M. F. Li , H. Y. Yu and D. -L. Kwong, " Modeling of Tunneling Currents Through HfO2 and (HfO2)x(Al2O3)1-x Gate Stacks," IEEE Electron Device Lett., vol. 24, no. 2, pp. 96 - 98 , 2003.
[4] D. H. Triyoso, R. I. Hegde, J. K. Schaeffer, R. Gregory, X.-D. Wang, M. Canonico, D. Roan, E. A. Hebert, K. Kim, J. Jiang, R. Rai, V. Kaushik, and S. B. Samavedam, “Characteristics of atomic-layer-deposited thin HfxZr1−xO2 gate dielectrics,” J. Vac. Sci. Technol. B, Microelectron. Process. Phenom., vol. 25, no. 3, pp. 845–852, May/Jun. 2007.
[5] G. D. Wilk, R. M. Wallace, and J. M. Anthony, “Hafnium and zirconium silicates for advanced gate dielectrics,” J. Appl. Phys., vol. 87, no. 1, pp. 484–492, 2000.
[6] K. Kyuno, K. Kita, and A. Toriumi, “Evolution of leakage paths in ... vacuum conducting atomic force microscopy,” Appl. Phys. Lett., vol. 86, no. 6, pp. 063510, Feb. 2005.
[7] E. Cartier, B. P. Linder, V. Narayanan, and V. K. Paruchuri, “Fundamental understanding and optimization of PBTI in nFETs with SiO2/HfO2 gate stack”, in IEDM Tech. Dig., 2006, pp. 321–324.
[8] M. Koyama, Y. Kamimuta, M. Koike, T. Ino, and A. Nishiyama, “Cubic-HfN formation in Hf-based high-κ gate dielectrics with N incorporation and its impact on electrical properties of films,” Jpn. J. Appl. Phys., vol. 44, no. 4B, pp. 2311, 2005.
[9] M. Terai, K. Watanabe, and S. Fujieda, “Effect of nitrogen profile and fluorine incorporation on negative bias temperature instability of ultrathin plasma nitrided SiON MOSFETs,” IEEE Trans. Electron Devices, vol. 54, no. 7, pp. 1658–1665, Jul. 2007.
[10] G. D. Wilk, and R. M. Wallace, “ Electrical properties of hafnium silicate gate dielectrics deposited directly on silicon,” Appl. Phys. Lett., vol. 74, pp. 2854, 1999.
[11] K. Kimura, S. Joumori, Y. Oota, K. Nakajima, and M. Suzuki, ”High resolution rbs: a powerful tool for atomic level characterization,” Nucl. Instr. and Meth. B vol. 351, pp. 219-220, 2004.
[12] G. Shang, P. W. Peacock, and J. Robertson, “Stability and band offsets of nitrogenated high-dielectric-constant gate oxides,” Appl. Phys. Lett., vol. 84, pp. 106-108, 2004.
[13] A. P. Huang, L. Wang, J. B. Xu and P. K. Chu, “Plasma Nitridated High-k Polycrystalline Array Induced by Electron Irradiation,” Nanotechnology, vol. 17, pp. 4379-4383, 2006.
[14] J. Huang, P. D. Kirsch, J. Oh, S. H. Lee, P. Majhi, H. R. arris, D. C. Gilmer, G. Bersuker, D. Heh, C. S. Park, C. Park, H. H. Tsenf, and R. Jammy , “Mechanisms Limiting EOT Scaling and Gate Leakage Currents of High-k/Metal Gate Stacks Directly on SiGe” IEEE Electron Device Lett., vol. 30, no. 3, pp.285-287 , 2009.
[15] Y. J. Cho, N. V. Nguyen, C. A. Richter, J. R. Ehrstein, B. H. Lee, and J. C. Lee , “Spectroscopic ellipsometry characterization of high-k dielectric HfO2 thin films and the high-temperature annealing effects on their optical properties, “ Appl. Phys. Lett., vol. 80, no. 7, pp. 1249-1251, Feb. 2002.
[16] S. Sayan, N. V. Nguyen, J. Ehrstein, J. J. Chambers, M. R. Visokay, M. A. Quevedo-Lopez, L. Colombo, D. Yoder, I. Levin, D. A. Fischer, M. Paunescu, O. Celik, and E. Garfunkel, “ Effect of nitrogen on band alignment in HfSiON gate dielectrics,“ Appl. Phys. Lett. vol. 87, 212905 pp. 1-3, 2005.
[17] J. Price, G. Bersuker, and P. S. Lysaght , “Identification of interfacial defects in high-k gate stack films by spectroscopic ellipsometry,” J. Vac. Sci. Technol. B vol. 27, pp. 310-312 , 2009.
[18] J. Price, G. Bersuker, P. S. Lysaght, and H. -H. Tseng, “Extending spectroscopic ellipsometry for identification of electrically active defects in Si/SiO2/high-k/metal gate stacks,” in Proc. VLSI- TSA. T55 pp. 61-62, 2009.

Chapter-6 References

[1] G. D. Wilk, R. M. Wallace, and J. M. Anthony, “High-κ gate dielectrics: Current status and materials properties considerations,” J. Appl. Phys., vol. 89, no. 10, p. 5243, May 2001.
[2] M. Koyama, A. Kaneko, T. Ino, M. Koike, Y. Kamata, R. Iijima, Y. Kamimuta, A. Takashima, M. Suzuki, C. Hongo, S. Inumiya, M. Takayanagi, and A. Nishiyama, “Effects of nitrogen in HfSiON gate dielectric on the electrical and thermal characteristics,” in IEDM Tech. Dig., 2002, pp. 849–852.
[3] C. H. Choi, S. J. Rhee,T. S. Jeon,N.Lu, J. H. Sim, R. Clark,M.Niwa, and D. L. Kwong, “Thermally stable CVD HfOxNy advanced gate dielectrics with poly-Si gate electrode,” in IEDM Tech. Dig., 2002, pp. 857–860.
[4] C. Choi, C. S. Kang, C. Y. Kang, S. J. Rhee, M. S. Akbar, S. A. Krishnan, M. Zhang, and J. C. Lee, “Positive bias temperature instability effects of Hf-based nMOSFETs with various nitrogen and silicon profiles,” IEEE Electron Device Lett., vol. 26, no. 1, pp. 32–34, Jan. 2005.
[5] M. S. Akbar, H.-J. Cho, R. Choi, C. S. Kang, C. Y. Kang, C. H. Choi, S. J. Rhee, Y. H. Kim, and J. C. Lee, “Optimized NH3 annealing process for high-quality HfSiON gate oxide,” IEEE Electron Device Lett., vol. 25, no. 7, pp. 465–467, Jul. 2004.
[6] G. Shang, P. W. Peacock, and J. Robertson, “Stability and band offsets of nitrogenated high-dielectric-constant gate oxides,” Appl. Phys. Lett., vol. 84, no. 1, pp. 106–108, Jan. 2004.
[7] J. L. Gavartin, A. L. Shluger, A. S. Foster, and G. I. Bersuker, “The role of nitrogen-related defects in high-κ dielectric oxides: Density-functional studies,” J. Appl. Phys., vol. 97, no. 5, p. 053 704, Mar. 2005.
[8] N. Umezawa, K. Shiraishi, T. Ohno, H. Watanabe, T. Chikyow, K. Torii, K. Yamabe, K. Yamada, H. Kitajima, and T. Arikado, “First-principles studies of the intrinsic effect of nitrogen atoms on reduction in gate leakage current through Hf-based high-κ dielectrics,” Appl. Phys. Lett., vol. 86, no. 14, p. 143 507, Apr. 2005.
[9] H. Takeuchi, D. Ha, and T.-J. King, “Observation of bulk HfO2 defects by spectroscopic ellipsometry,” J. Vac. Sci. Technol. A, Vac. Surf. Films, vol. 22, no. 4, pp. 1337–1341, Jul. 2004.
[10] K. Torii, K. Shiraishi, S. Miyazaki, K. Yamabe, M. Boero, T. Chikyow, K. Yamada, H. Kitajima, and T. Arikado, “Physical model of BTI, TDDB and SILC in HfO2-based high-κ gate dielectrics,” in IEDM Tech. Dig., 2004, pp. 129–132.
[11] H. Watanabe, S. Kamiyama, N. Umezawa, K. Shiraishi, S. Yoshida, Y. Watanabe, T. Arikado, T. Chikyow, K. Yamada, and K. Yasutake, “Role of nitrogen incorporation into Hf-based high-κ gate dielectrics for termination of local current leakage paths,” Jpn. J. Appl. Phys., vol. 44, no. 43, p. L1333, 2005.
[12] Y. P. Feng, A. T. L. Lim, and M. F. Li, “Negative-U property of oxygen vacancy in cubic HfO2,” Appl. Phys. Lett., vol. 87, no. 6, p. 062 105, Aug. 2005.
[13] K. Xiong, J. Robertson, M. C. Gibson, and S. J. Clark, “Defect energy levels in HfO2 high-dielectric-constant gate oxide,” Appl. Phys. Lett., vol. 87, no. 18, p. 183 505, Oct. 2005.
[14] K. Xiong, J. Robertson, and S. J. Clark, “Passivation of oxygen vacancy states in HfO2 by nitrogen,” J. Appl. Phys., vol. 99, no. 4, p. 044 105, Feb. 2006.