1 Open Access

Electronic Synapses Enabled by an Epitaxial SrTiO3-δ / Hf0.5Zr0.5O2 Ferroelectric Field-Effect Memristor Integrated on Silicon

Siannas, N; Zacharaki, C; Tsipas, P; Kim, DJ; Hamouda, W; Istrate, C; Pintilie, L; Schmidbauer, M; Dubourdieu, C; Dimoulas, A

FEB 2024, ADVANCED FUNCTIONAL MATERIALS, 34

DOI: 10.1002/adfm.202311767

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Synapses play a vital role in information processing, learning, and memory formation in the brain. By emulating the behavior of biological synapses, electronic synaptic devices hold the promise of enabling high-performance, energy-efficient, and scalable neuromorphic computing. Ferroelectric memristive devices integrate the characteristics of both ferroelectric and memristive materials and present a far-reaching potential as artificial synapses. Here, it is reported on a new ferroelectric device on silicon, a field-effect memristor, consisting of an epitaxial ultrathin ferroelectric Hf(0.5)Z(r0.5)O(2) film sandwiched between an epitaxial highly doped oxide semiconductor SrTiO3-delta and a top metal. Upon a low voltage of less than 2 V, the field-effect modulation in the semiconductor enables to access multiple states. The device works in a large time domain ranging from milliseconds down to tens of nanoseconds. By gradually switching the polarization by identical pulses, the ferroelectric diode devices can dynamically adjust the synaptic strength to mimic short- and long-term memory plasticity. Ionic contributions due to redox processes in the oxide semiconductor beneficially influence the device operation and retention.

2 Open Access

Metastable ferroelectricity driven by depolarization fields in ultrathin Hf0.5Zr0.5O2

Siannas, N; Zacharaki, C; Tsipas, P; Chaitoglou, S; Bégon-Lours, L; Istrate, C; Pintilie, L; Dimoulas, A

JUL 6 2022, COMMUNICATIONS PHYSICS, 5, 178

DOI: 10.1038/s42005-022-00951-x

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As ferroelectric Hf0.5Zr0.5O2 (HZO) thickness scales below 10 nm, the switching characteristics are severely distorted typically showing an antiferroelectric-like behavior (pinched hysteresis) with reduced remanent polarization. Using Landau-Ginsburg-Devonshire (LGD) theory for the analysis of the experimental results, it is shown here that, in thin (5 nm) HZO, depolarization fields drive the system in a stable paraelectric phase coexisting with a metastable ferroelectric one, which explains the pinched hysteresis. This state of matter resembles a first order ferroelectric above the Curie temperature which is known to result in similar double-loop behavior. Here, based on the analysis of experimental data in the framework of LGD theory, it is reported that charge injection and trapping at pre-existing interface defects during field cycling ("wake-up") screens the depolarization field stabilizing ferroelectricity. It is found in particular that a sufficiently large energy density of interface states is beneficial for the recovery of fully open ferroelectric loops. HfO2-based ferroelectric materials have immense technological potential and so significant attention has been given to improve the ferroelectric properties at low-thickness. Here, using Landau Devonshire theory, the authors show the origin of pinched hysteresis loops is connected with the existence of pronounced depolarizing fields which are minimized during field cycling recovering the full ferroelectric loops.

3

The Role of Interface Defect States in n- and p-Type Ge Metal-Ferroelectric-Semiconductor Structures with Hf0.5Zr0.5O2 Ferroelectric

Boni, GA; Istrate, CM; Zacharaki, C; Tsipas, P; Chaitoglou, S; Evangelou, EK; Dimoulas, A; Pintilie, I; Pintilie, L

FEB 2021, PHYSICA STATUS SOLIDI A-APPLICATIONS AND MATERIALS SCIENCE, 218, 2000500

DOI: 10.1002/pssa.202000500

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The discovery of ferroelectricity in doped HfO2 represents an excellent opportunity to overcome the obstacles in manufacturing reliable ferroelectric field effect transistors (FeFET) for nonvolatile memory applications, considering that HfO2 is compatible with Si and Ge and it is already used in semiconductor industry. The presence of interface defects may have detrimental effects on the operation of FeFETs, so their role is systematically investigated in this study in correlation with the substrate doping. Metal-ferroelectric-semiconductor (MFS) structures are fabricated by depositing Hf0.5Zr0.5O2 (HZO) layers on n-type Ge substrate. Their electric properties are compared with those of MFS structures obtained by depositing HZO on p-type Ge, to study the influence of the doping. It is found that, although the ferroelectric properties of HZO are similar, the capacitance and impedance of the MFS structures behave differently. For n-Ge, the occupation probability of a large number of low-lying interface defect acceptor states, charges the interface negatively which adversely affects the C-V response of the MFS, albeit without harming the ferroelectric (P-V) hysteresis. Although the interface defects do not harm ferroelectricity, they could inhibit inversion in p-type Ge or accumulation in n-type Ge so they should be taken into account when designing Ge FeFET devices.

4 Open Access

Depletion induced depolarization field in Hf1-xZrxO2 metal-ferroelectric-semiconductor capacitors on germanium

Zacharaki, C; Tsipas, P; Chaitoglou, S; Evangelou, EK; Istrate, CM; Pintilie, L; Dimoulas, A

MAY 4 2020, APPLIED PHYSICS LETTERS, 116

DOI: 10.1063/5.0007111

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Germanium Metal-Ferroelectric-Semiconductor (MFS) capacitors based on ferroelectric Hf1-xZrxO2 (HZO) with clean, oxide free Ge/HZO interfaces emerge as an interesting layer structure for the fabrication of ferroelectric field effect transistor (FeFET) non-volatile memory devices. It is shown that, at low temperature (<160K), a semiconductor depletion forms in Ge near the interface, resulting in an increase in coercive voltage by about 2V, accompanied by a distortion of the ferroelectric hysteresis with subloop asymmetric behavior, which becomes more severe at higher frequencies of measurement. At higher temperatures, the Ge surface near the ferroelectric is easily inverted due to the low energy gap of Ge, providing sufficient screening of the polarization charge by minority free carriers, in which case, nearly ideal, symmetric hysteresis curves are recovered. The depolarization field is experimentally extracted from the coercive voltage and the capacitance measurements, is found to be 2.2MV/cm in the low temperature range, comparable to the coercive field, then rapidly decreases at higher temperatures, and effectively diminishes at room temperature. This makes Ge MFSs good candidates for FeFETs for low voltage non-volatile memory with improved reliability.

5

Very large remanent polarization in ferroelectric Hf1-xZrxO2 grown on Ge substrates by plasma assisted atomic oxygen deposition

Zacharaki, C; Tsipas, P; Chaitoglou, S; Fragkos, S; Axiotis, M; Lagoyiannis, A; Negrea, R; Pintilie, L; Dimoulas, A

MAR 18 2019, APPLIED PHYSICS LETTERS, 114

DOI: 10.1063/1.5090036

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Plasma assisted atomic oxygen deposition was used to grow polycrystalline ferroelectric Hf1-xZrxO2 (x = 0.5-0.7) on technologically important (100) Germanium substrates showing sharp crystalline interfaces free of interfacial amorphous layers and strong evidence for the presence of a predominately orthorhombic phase. The electrical properties, evaluated using metal-ferroelectric-semiconductor (MFS) capacitors, show symmetric and robust ferroelectric hysteresis with weak or no wake-up effects. The MFS capacitors with x = 0.58 show very large remanent polarization up to 34.4 mu C/cm(2) or 30.6 mu C/cm(2) after correction for leakage and parasitics, combined with good endurance reaching 10(5) cycles at a cycling field of 2.3 MV/cm. The results show good prospects for the fabrication of Ge ferroelectric field effect transistors (FeFETs) for use in 1 T FeFET embedded nonvolatile memory cells with improved endurance. (C) 2019 Author(s).

6

Electrical properties of as-grown molecular beam epitaxy high-k gate dielectrics deposited on silicon

Goldenblum, A; Pintilie, I; Buda, M; Popa, A; Lisca, M; Botila, T; Teodorescu, V; Dimoulas, A; Vellianitis, G

MAR 15 2006, JOURNAL OF APPLIED PHYSICS, 99

DOI: 10.1063/1.2180428

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The carrier transport mechanisms in as-grown LaAlO3 and La2Hf2O7 high-k insulator layers deposited on n- and p-Si were deduced from temperature dependent C-V and I-V characteristics correlated with photoelectric measurements. Large, parallel shifts in the high frequency C-V curves are explained by the presence of a large density of interface states and an approximate analytical formula relating the density of states to the C-V shift is deduced. The space charge limited current is explained by the existence of impurity channels situated energetically near the conduction or valence band of silicon.

7

Interface trap density in amorphous La2Hf2O7/SiO2 high-kappa gate stacks on Si

Mereu, B; Dimoulas, A; Vellianitis, G; Apostolopoulos, G; Scholz, R; Alexe, M

FEB 2005, APPLIED PHYSICS A-MATERIALS SCIENCE & PROCESSING, 80, 257

DOI: 10.1007/s00339-004-2910-9

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The present paper investigates the interface trap density of a new high-kappa gate dielectric stack, La2Hf2O7/SiO2 on Silicon. Amorphous La2Hf2O7 thin films are deposited by metal evaporation in the presence of atomic oxygen beams on an ultra-thin SiO2 layer (1.5 nm) grown by rapid thermal oxidation on a p-type Si substrate. A combination of electrical (C-V) and cross sectional TEM measurements indicates a value of the dielectric constant kappa of about 19 +/- 2.2. The interface states density (D-it) was measured using the conductance method for different La2Hf2O7 thicknesses ranging from 3 nm to 14 nm. Dit ranges from 3.4 x 10(10) eV(-1) cm(-2) to 4.8 x 10(12) eV(-1) cm(-2) and shows a quasi-linear dependence on the La2Hf2O7 layer thickness. The interface state density increase with film thickness could have different explanations, such as oxygen de-passivation and/or defect generation at the Si-SiO2 interface, formation of a new Si-SiO2 interface by Si oxidation or alternatively, the SiO2 interfacial layer reduction by oxygen vacancies.

8

Space-charge-limited current involving carrier injection into impurity bands of high-k insulators

Goldenblum, A; Pintilie, I; Buda, M; Popa, A; Botila, T; Dimoulas, A; Vellianitis, G

MAY 16 2005, APPLIED PHYSICS LETTERS, 86

DOI: 10.1063/1.1935045

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Photoelectrical measurements have shown that the current flow through La2Hf2O7 and LaAlO3 high-k insulator layers deposited on silicon takes place via impurity channels. A space charge limited current is evidenced, for different insulator thicknesses and temperatures, by the square law dependence of current versus voltage. The analysis demonstrates that this space charge limited (SCL) current in thin insulator films can be explained only by the presence of impurity channels situated near the Fermi level of the injecting contact. Many other aspects related to the SCL current behavior were found. (c) 2005 American Institute of Physics.

9

Electrical properties of metal-oxide-silicon structures with LaAlO3 as gate oxide

Mereu, B; Sarau, G; Dimoulas, A; Apostolopoulos, G; Pintilie, I; Botila, T; Pintilie, L; Alexe, A

JUN 15 2004, MATERIALS SCIENCE AND ENGINEERING B-SOLID STATE MATERIALS FOR ADVANCED TECHNOLOGY, 109, 98

DOI: 10.1016/j.mseb.2003.10.054

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In this paper, electrical investigations performed on complex metal-oxide-semiconductor (MOS) structures with amorphous LaAlO3 deposited as gate oxide on a rapid thermal processed SiO2 buffer layer are presented. Current-voltage (I-V) measurements at different temperatures and high frequency room-temperature capacitance-voltage (C-V measurements indicate the presence of a non-equilibrium state in p-type Si (100) substrate under reverse polarization of the structure. The asymmetry in I-V characteristics is opposite to the expected one for the high-kappa/interfacial layer stack behavior. Different indications for the non-equilibrium MOS state are inferred from the experimental data, and the extraction of MOS physical parameters by using the classical C-V method is shown to be unreliable. For small and large applied forward voltages defect-related charge transport and tunneling currents dominate, respectively. (C) 2003 Elsevier B.V. All rights reserved.

10

The Role of Interface Defect States in n- and p-Type Ge Metal-Ferroelectric-Semiconductor Structures with Hf0.5Zr0.5O2 Ferroelectric

Boni, GA; Istrate, CM; Zacharaki, C; Tsipas, P; Chaitoglou, S; Evangelou, EK; Dimoulas, A; Pintilie, I; Pintilie, L

, PHYSICA STATUS SOLIDI A-APPLICATIONS AND MATERIALS SCIENCE, 2000500

DOI: 10.1002/pssa.202000500

Show abstract

The discovery of ferroelectricity in doped HfO2 represents an excellent opportunity to overcome the obstacles in manufacturing reliable ferroelectric field effect transistors (FeFET) for nonvolatile memory applications, considering that HfO2 is compatible with Si and Ge and it is already used in semiconductor industry. The presence of interface defects may have detrimental effects on the operation of FeFETs, so their role is systematically investigated in this study in correlation with the substrate doping. Metal-ferroelectric-semiconductor (MFS) structures are fabricated by depositing Hf0.5Zr0.5O2 (HZO) layers on n-type Ge substrate. Their electric properties are compared with those of MFS structures obtained by depositing HZO on p-type Ge, to study the influence of the doping. It is found that, although the ferroelectric properties of HZO are similar, the capacitance and impedance of the MFS structures behave differently. For n-Ge, the occupation probability of a large number of low-lying interface defect acceptor states, charges the interface negatively which adversely affects the C-V response of the MFS, albeit without harming the ferroelectric (P-V) hysteresis. Although the interface defects do not harm ferroelectricity, they could inhibit inversion in p-type Ge or accumulation in n-type Ge so they should be taken into account when designing Ge FeFET devices.