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Explanation of the Charge-Trapping Properties of Silicon Nitride Storage IEEE TRANSACTIONS ON ELECTRON DEVICES, VOL. 58, NO. 8, AUGUST 2011 2483 Explanation of the Charge-Trapping Properties of Silicon Nitride Storage Layers for NVM Devices Part I: Experimental Evidences From Physical and Electrical Characterizations Elisa Vianello, Francesco Driussi, L. Perniola, Gabriel Molas, Jean-Philippe Colonna, B. De Salvo, and Luca Selmi Abstract—In part I of this paper, we study the physicochemical and their superior scaling capabilities compared with standard structure and the electrical properties of low-pressure-chemical- floating-gate Flash memory devices. Moreover, the program vapor-deposited silicon nitride (SiN) aimed to serve as storage and erase (P/E) operation by hot carriers and the possibility of layers for nonvolatile memory applications. An in-depth material analysis has been carried out together with a comprehensive multibit storage can be exploited to further increase the storage electrical characterization on two samples fabricated with recipes density [5], [6]. yielding rather standard SiN and Si-rich SiN. The investigation However, ultimately optimized cells have not been defined points out the impact of SiN stoichiometry and hydrogen content yet, and many alternative device structures have been recently on the electrical characteristics of gate stacks designed in view of proposed to improve WRITE, erase, and retention times [7], channel hot-electron/hole-injection program/erase (P/E) operation and tunnel P/E operation. The extensive and detailed characteriza- [8]. In particular, the optimization of the performance of tion establishes a sound experimental basis for the development of SONOS/MANOS cells is constrained by the tradeoff between the physics-based trap models proposed in the companion paper. the erase speed and the charge loss through the tunnel and top Index Terms—Charge trapping, nonvolatile memory devices, oxides during retention at high temperatures [9]–[11]. Instead, silicon nitride (SiN). in cells that are programmed/erased by the localized injection of hot carriers, the lateral charge drift and the recombination of the trapped charge are particularly worrisome because they give I. INTRODUCTION rise to data-retention issues [5], [12]–[14]. HARGE-TRAP nonvolatile memory devices based on The SiN composition plays a fundamental role on the per- C silicon nitride (SiN) storage layers are good candi- formance and reliability of the memory cells [8], [15]–[17]. dates to extend the current floating-gate technologies beyond The understanding of the electrical properties of SiN films with the 22-nm node [1]. In particular, metal-gate–Al2O3–nitride– different stoichiometry thus is of great importance in order to oxide–silicon (MANOS) devices are widely studied in the optimize the charge-trap memory technologies. Nevertheless, literature as a solution for a NAND architecture [2]–[4], which no clear and in-depth physical explanation of the impact of SiN is due to their intrinsic robustness to defects in the tunnel oxide composition on the memory behavior has been achieved yet. To shed new light on this relevant topic, we extended and completed the material analysis and the device characterization Manuscript received June 18, 2010; revised November 12, 2010, January 20, partly reported in [18]–[20] by carrying out a thorough study 2011, and March 21, 2011; accepted March 23, 2011. Date of publication of the chemical composition and the material structure of SiN May 2, 2011; date of current version July 22, 2011. This work was supported in part by the French Public Authorities through the NANO 2012 Program; layers deposited with different recipes by means of physical, by the Italian Ministry of Information, University, and Research through chemical, and electrical characterizations (e.g., secondary ion the Basic Research Investment Fund under Project RBIP06YSJ; and by the mass spectometry (SIMS), multiple internal reflection (MIR) European Union through the Seventh Framework Programme under Contract 214431 “GOSSAMER.” The review of this paper was arranged by Editor spectroscopy, spectroscopic ellipsometry, X-ray reflectometry, H. S. Momose. capacitance–voltage (C–V ) measurements, etc.), in order to E. Vianello is with the Department of Electrical, Management and Me- chanical Engineering, University of Udine, 33100 Udine, Italy, and also better understand the carrier transport and trapping character- with the Atomic and Laboratory of Electronics, Technology, and Instru- istics of the SiN storage layers. Furthermore, we investigated mentation, Atomic and Alternative Energies Commission, Micro and Nano- the operation of memory test structures with two distinctly technology Innovation Centre Campus, 38054 Grenoble Cedex 9, France (e-mail: [email protected]). different SiN films, particularly suited to study the impact of F. Driussi and L. Selmi are with the the Department of Electrical, Manage- SiN stoichiometry on the program/erase/retention characteris- ment, and Mechanical Engineering, University of Udine, 33100 Udine, Italy. tics of both MANOS test structures (i.e., written and erased L. Perniola, G. Molas, J.-P. Colonna, and B. De Salvo are with the Atomic and Laboratory of Electronics, Technology, and Instrumentation, Atomic and by tunneling) and thick tunnel-oxide test structures written by Alternative Energies Commission, Micro and Nanotechnology Innovation channel hot electrons (CHEs) and erased by hot-hole injection Centre Campus Campus, 38054 Grenoble Cedex 9, France. (HHI). The experimental data suggest that the SiN composition Color versions of one or more of the figures in this paper are available online at http://ieeexplore.ieee.org. does not alter appreciably the density and energy of the traps Digital Object Identifier 10.1109/TED.2011.2140116 with respect to the bottom of the SiN conduction band. 0018-9383/$26.00 © 2011 IEEE 2484 IEEE TRANSACTIONS ON ELECTRON DEVICES, VOL. 58, NO. 8, AUGUST 2011 TABLE I PROCESS PARAMETERS FOR THE SiN FABRICATION RECIPES USED IN THIS PAPER.THE GAS FLOWS ARE MEASURED IN STANDARD CUBIC CENTIMETER PER MINUTE (SCCM) In part II of this paper, we exploit atomistic- and device- level simulations to develop, with the help of the experiments, realistic models of the SiN films. The models suggest a simple Fig. 1. Immaginary part of the dielectric constant obtained from spectroscopic ellipsometry spectra and experimentally extracted values of the bandgap of std interpretation of the electrical properties of films with different and Si-rich SiN. SiN compositions, which is then confirmed experimentally. II. CHARACTERIZATION OF THE LPCVD SiN LAYERS Thin SiN films have been fabricated by low-pressure chemical-vapor deposition (LPCVD), i.e., with two different recipes, to produce relatively standard (std) and silicon-rich (Si-rich) SiN films. The main process parameters are reported in Table I. In particular, the SiN composition has been modulated by varying the precursor gas-flow ratio R =[SiH2Cl2]/[NH3]. The std SiN films have been grown at R = 0.1 sccm, whereas for the slightly Si-rich samples, R = 5 sccm has been chosen. The std film turned out to be stoichiometric Si3N4 within an accuracy value of 3%. The recipes have been used to deposit 6-nm-thick std and Si-rich SiN films on flat wafers for the material analysis with physicochemical measurements. In order to emulate the thermal processes involved in the fabrication of the source/drain (S/D) implants in full devices, a rapid anneal of ≈1 min at 1050 ◦C has been performed as well. A. Physicochemical Analysis The composition and the structure of the SiN layers grown on the flat wafers have been studied by means of different experi- mental techniques. First, we performed spectroscopic ellipsom- etry on nearly stoichiometric SiN and the films enriched with Fig. 2. (a) SIMS distributions of elements along the vertical direction of excess silicon, obtaining a refractive index of 2 and 2.4, respec- the structure with std SiN after baking at 1050 ◦C. Note the presence of a tively, i.e., in agreement with the literature data [21], [22]. Fig. 1 considerable amount of hydrogen in the SiN layer. Note that the SIMS profiles shows the imaginary part of the dielectric function 2 obtained of the different species are not directly quantitatively comparable because, to be translated in an element concentration, they need relative sensitivity from the spectroscopic ellipsometry spectra and the calculated factors that are dependent on the considered species. (b) Comparison of the bandgap-energy value EG for the std and Si-rich samples [8]. H concentrations obtained with the SIMS and MIR measurements in std and It is worth pointing out that annealing has no significant effect Si-rich SiN before and after baking. on the EG value (not shown). The bandgap of std SiN is ≈5.3 eV, which is in agreement with previously published interfaces between the layers, and it is possible to see the piling results of a nearly stoichiometric (noncrystalline) LPCVD SiN up of hydrogen in the bulk of the SiN layer [25], which we layer, which is obtained by X-ray photoelectron spectroscopy found to be present both before and after the S/D annealing and Bremsstrahlung isochromat spectroscopy [23], [24]. The step (not shown) [18]. The SIMS measurements also show that excess silicon reduces the energy bandgap to a value of about the oxygen content inside the SiN bulk is very limited and it is 4.7 eV, which is consistent with [8]. identical in the std and Si-rich SiN films (not shown). Fig. 2(b) Fig. 2(a) shows the SIMS distribution of elements, i.e., after (white bars) shows the ratio between the secondary ion intensity baking at 1050 ◦C, which is along a gate-stack structure with values for the H and Si atoms, and it is worth noting that the H std SiN. The vertical lines show the estimated positions of the atoms are present in both SiN recipes, although the H content VIANELLO et al.: CHARGE-TRAPPING PROPERTIES OF SIN LAYERS FOR NVM DEVICES I 2485 TABLE II N–H AND Si–H BOND CONCENTRATIONS ESTIMATED FROM THE ABSORPTION BANDS OF THE STRETCHING LOCAL VIBRATIONAL MODES OF N–H AND Si–H BONDS MEASURED BY MIR.
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