Experimental and Theoretical Study of Electrode Effects in HfO2 based RRAM
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1 Experimental and Theoretical Study of Electrode Effects in HfO2 based RRAM C. Cagli 1, J. Buckley 1, V. Jousseaume 1, T. Cabout 1, A. Salaun 1, H. Grampeix 1, J. F. Nodin 1,H. Feldis 1, A. Persico 1, J. Cluzel 1, P. Lorenzi 6, L. Massari 6, R. Rao 6, F. Irrera 6, F. Aussenac 1, C. Carabasse 1, M. Coue 1, P. Calka 1, E. Martinez 1, L. Perniola 1, P. Blaise 1, Z.Fang 2, Y. H. Yu 2, G. Ghibaudo 3, D. Deleruyelle 4, M. Bocquet 4, C. Müller 4, A. Padovani 5, O. Pirrotta 5, L. Vandelli 5, L. Larcher 5, G. Reimbold 1, B. de Salvo 1 1 CEA-LETI, MINATEC, Grenoble, France 2 School of Electrical and Electronic Engineering, Nanyang Technological University,Singapore, 3 IMEP-CNRS, MINATEC, Grenoble France, 4 IM2NP, UMR CNRS 6242, Aix-Marseille Universite, Marseille, France, 5 DISMI - Università di Modena e Reggio Emilia, Reggio Emilia, Italy, 6 Università "La Sapienza", Roma, Italy
2 Outline Introduction Experimental evidences Interface layer Quasi-static characterization Scaling Activation energy for conduction Set dynamics Noise measurements Data retention Modeling and calculations Unipolar set/reset model Ab-initio calculations Forming modeling Conclusions
3 High CMOS compatibility Low voltage (< 2.5V) High speed (100ns) BEOL integration Low cost High density potential Crossbar possibility 3D stack potential Introduction HfO 2 is a very promising candidate However: 1. Switching mechanism in HfO 2 unclear 2. Impact of electrodes not yet assessed: 1. non-polar vs. bipolar 2. impact on working potentials 3. data retention 1D1R device Electronic irresistible memory, Samsung and Sejong University, NGP Asia Materials,
4 Samples description TiN (50nm) V V Ti (10nm) Pt 25nm Ti 5nm Interfacial layer Pt 25nm Ti 10nm Interfacial layer HfO2 10nm Pt 25nm HfO2 10nm Pt 25nm HfO2 10nm Interfacial layer TiN 25nm HfO2 10nm TiN 25nm TiN (10nm) V ALD (350 C) poly crystalline HfO 2 with 4 different PVD electrode patterns HfO2 on Pt found monoclinic, while mainly orthorhombic on TiN Ti(10nm)/TiN(50nm) encapsulation ; Pt(25nm)/Ti/TiN for Ti-based samples. Interfacial layer spontaneously formed at Ti-HfO 2 Different polarity character observed 2
5 Physicochemical analysis (EDX) Pt Hf Ti O Position Ti Interfacial layer HfO2 Pt EDX Analysis reveals O displacement toward Ti. Interfacial layer produced by the Ti O-getter character. O-poor HfO2 layer arose. 3
6 Physicochemical analysis (EDX) Pt Hf Ti O Position Ti Interfacial layer HfO2 Pt EDX Analysis reveals O displacement toward Ti. Interfacial layer produced by the Ti O-getter character. O-poor HfO2 layer arose. 3
7 Electrodes impact on polarity Ti found to initiate the bipolar character of the RRAM device 4
8 Electrode comparison V forming [V] V SET [V] V RESET [V] R SET [Ω] R RESET [Ω] NON-POLAR BEHAVIOUR Pt-Pt 4.4 ± ± ± 0.15 <100 ~1M BIPOLAR BEHAVIOUR Pt-Pt 4.7 ± ± ± 0.1 ~ M Pt-Ti 1.35 ± ± ± 0.1 ~800 10k-1M TiN-Pt 3.75 ± ± ± k-1M TiN-Ti 1.90 ± ± ± 0.2 ~400 6K-20K Positive impact of Ti electrodes: Lower forming voltage Lower set voltage Negative impact: Higher reset voltage (but NOT for TiN-Ti) Higher ON resistance on TiN-Ti stack 5
9 Electrode comparison V forming [V] V SET [V] V RESET [V] R SET [Ω] R RESET [Ω] NON-POLAR BEHAVIOUR Pt-Pt 4.4 ± ± ± 0.15 <100 ~1M BIPOLAR BEHAVIOUR Pt-Pt 4.7 ± ± ± 0.1 ~ M Pt-Ti 1.35 ± ± ± 0.1 ~800 10k-1M TiN-Pt 3.75 ± ± ± k-1M TiN-Ti 1.90 ± ± ± 0.2 ~400 6K-20K Positive impact of Ti electrodes: Lower forming voltage Lower set voltage Negative impact: Higher reset voltage (but NOT for TiN-Ti) Higher ON resistance on TiN-Ti stack 5
10 Electrode comparison V forming [V] V SET [V] V RESET [V] R SET [Ω] R RESET [Ω] NON-POLAR BEHAVIOUR Pt-Pt 4.4 ± ± ± 0.15 <100 ~1M BIPOLAR BEHAVIOUR Pt-Pt 4.7 ± ± ± 0.1 ~ M Pt-Ti 1.35 ± ± ± 0.1 ~800 10k-1M TiN-Pt 3.75 ± ± ± k-1M TiN-Ti 1.90 ± ± ± 0.2 ~400 6K-20K Positive impact of Ti electrodes: Lower forming voltage Lower set voltage Negative impact: Higher reset voltage (but NOT for TiN-Ti) Higher ON resistance on TiN-Ti stack 5
11 Area scaling SET OFF TiN-Ti sample ON RESET No area-scaling effect in accordance with filament-like conduction mechanism 6
12 Conduction mechanism R( T ) = R0 exp E kt AC As previously observed on Pt/NiO/Pt, there is a continuum between ON states -metallic- and OFF states -semiconductor- in accordance with filament-like/localized conduction picture 7
13 Set dynamics V A V Set V cell Set voltage measured as a function of the ramp speed 9
14 Set dynamics The Ti presence strongly reduces both the set voltage and its variability 10
15 Data retention 250 C on TiN-Ti Fail time Positive impact of Ti in data retention performances No soldering reflow issues (260 C hundreds of sec. ) 11
16 Ab-initio calculations DOS Calculated with SIESTA (DFT) 50 E F energy DOS [nb state ev -1 ] Energy [ev] States in the gap appear in case of O-vacancy presence O-vacancy alignment could explain conduction across HfO 2 12
17 SET-RESET model Current [A] CF Voltage [V] SET RESET For Non-polar case (Pt-Pt) simple redox-based model accounts for SET Self-heating induced dissolution model accounts for RESET 13
18 Forming modeling Data Sims - Total current Sims Dominant GB Forming assumed to occur across a Grain Boundary (GB) Field-temperature driven defects generation leads to CF Model accounts for forming IV curves 14
19 Forming modeling Data Sims - Total current Sims Dominant GB Ti effect modeled with additional O-poor layer with lower defect generation energy cost The model account for V forming reduction 15
20 Conclusions Filament-like formation/disruption of a conductive path proved to be the switching mechanism in HfO 2 -based RRAM devices Ti O-getter character spotted out as responsible of bipolar switching mode initiation Impact of Ti (and TiN) electrodes evaluated: Forming and set voltages lowering Data retention improvement Ab-initio calculations, unipolar switching model and forming model provided
21 Backup
22 Physico-chemical analysis Pt HfO2 Interfacial layer TiN
23 Introduction metal insulator metal Forming Set ON State Reset OFF State Reversible switching between two differently resistive states Many different oxides (NiO, HfO2, TiO, TaO,..) and electrodes (Pt, Au, Ti, TiN, W, ) are possible Non-polar or bipolar mode possible
24 Introduction V Pt HfO2 Pt Programming by voltage ramps or voltage pulses Current compliance exploited during set to prevent hard breakdown
25 Endurance OFF states ON states
26 In literature Fully CMOS BEOL compatible HfO2 RRAM cell, with low (µa) program current, strong retention and high calability, using an optimized Plasma Enhanced Atomic Layer Deposition (PEALD) process for TiN electrode IEEE, IITC: Y.Y.Chen* [1,2], L. Goux [1], L. Pantisano[1], et al. IMEC, 2011 Leti Ti/TiN
27 IV-curves Set Current [A] Reset Forming TiN-Ti Voltage [V] High reproducibility of IV curves
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