SiGeSn nanocrystals with charge storage properties at nanoscale – SIGESNANOMEM
Project Director: Dr. Ana Maria Lepadatu
For project webpage in Romanian click here
Project ID: 19 from 1/05/2018 (PN-III-P1-1.1-TE-2016-2366)
Project Director: Dr. Ana-Maria Lepadatu
Project Type: National
Project Program: TE
Funded by: Romanian National Authority for Scientific Research, UEFISCDI
Contractor: National Institute of Materials Physics
Project Status: In progress
Start Date: Wednesday, May 1, 2019
End Date: Friday, April 30, 2021
SIGESNANOMEM Project Abstract:
The project aims to obtain nanostructured materials based on SiGeSn nanocrystals (NCs) embedded in oxide matrix with charge storage properties for non-volatile memory applications. The material is completely new, beyond the state of the art as no reports on SiGeSn NCs in oxides are to be found in literature. The project goal will be achieved by 5 specific objectives: O1) obtaining trilayer capacitors with the floating gate of SiGeSn NCs embedded in oxide matrix (SiO2, HfO2) by magnetron sputtering deposition and nanostructuring by thermal annealing; O2) morphology and structure characterisation of NCs-based trilayers for optimizing technological parameters; O3) investigation of electrical and charge storage properties and their correlation with structure and morphology; O4) evaluation of memory parameters of SiGeSn NCs based capacitors in function of NCs morphology and composition; O5) dissemination of project results. For this, the trilayer approach will be used aiming to obtain memory capacitor-like structures with floating gate based on SiGeSn NCs playing the role of charge storage nodes, the NCs having optimal size and density, being properly positioned in respect to Si substrate at tunnelable distance as well as being well separated to each other. More than that, the SiGeSn NCs spatial distribution in the floating gate will be optimized for obtaining a 2D array. The memory properties (memory window and retention) will be controlled by varying the NCs composition and size, by obtaining tunnel oxide with high material quality and proper thickness. The good and complementary expertise of team members ensures the implantation of project in a thematic beyond the state of the art. The original scientific results will be published in 5 papers in high impact ISI-ranked journals and presented at prestigious international conferences.
Obtaining nanostructured materials based on SiGeSn NCs with charge storage properties by convenient modification of the morphology of trilayer structures and NCs composition. The obtaining of a floating gate with SiGeSn NCs arranged in a 2D array is targeted.
Dr. A.M. Lepadatu - Project Director
Dr. I. Stavarache
Dr. V.A. Maraloiu
Dr. A. Slav
Dr. C. Palade
Assessment of Project Implementation - SUMMARY
Project SIGESNANOMEM aimed to obtain nanostructured materials (3-layer structures) based on SiGeSn nanocrystals (NCs) embedded in oxide matrix with charge storage properties for non-volatile memory applications. 3-layer structures are MOS-like and have configuration of gate oxide/ floating gate of SiGeSn NCs embedded in oxide / tunnel oxide / p-Si substrate, the chosen oxide (Stage I / 2019) being HfO2; SiGeSn NCs play the role of charge storage nodes, being positioned at tunnelable distance from the p-Si substrate in order to ensure charge injection. The charge storage properties were adjusted by modification of 3-layer structure morphology and SiGeSn NC composition by both modifying & adjusting deposition parameters (composition of SiGeSn-HfO2 intermediate layer, layers thicknesses etc.) during Stage I / 2019 and Stage II / 2020 and varying & adjusting RTA annealing parameters for nanostructuring (temperature & duration) during whole project.
The project aim was achieved by following 5 specific objectives:
O1) obtaining 3-layer capacitors with floating gate of SiGeSn NCs embedded in oxide matrix of HfO2 by magnetron sputtering deposition and nanostructuring by thermal annealing;
O2) morphology & structure characterisation of NCs-based 3-layers for optimizing technological parameters;
O3) investigation of electrical & charge storage properties and their correlation with structure & morphology;
O4) evaluation of memory parameters of SiGeSn NCs based capacitors in function of NCs morphology & composition;
O5) dissemination of project results.
Project implementation was carried out in 3 stages:
Stage I / 2019 Preparation of test memory structures based on SiGeSn NCs;
Stage II / 2020 Preparation & complex characterization of oxide/SiGeSn-oxide/oxide/Si substrate 3-layer structures;
Stage III/2021 Modelling of MOS capacitors with SiGeSn NCs based floating gate.
The expected results were obtained:
(i) Capacitor structures with intermediate layer of SiGeSn NCs in HfO2: the optimal deposition configuration of gate HfO2/ SiGeSn-HfO2 / tunnel HfO2 / p-Si substrate was found in which the intermediate layer / floating gate is obtained by co-sputtering SiGeSn-HfO2 – Stage I / 2019; later, the technological parameters for preparation were adjusted, i.e. SiGeSn-HfO2 composition of intermediate layer, thicknesses of the 3 component layers – Stage II / 2020 and RTA annealing temperature – Stage II / 2020, Stage III / 2021; SiGeSn NCs were evidenced by (HR)TEM, Raman spectroscopy and XRD, and their composition and diameter was evaluated – Stage I / 2019, Stage II / 2020.
(ii) Electrical characteristics: frequency dispersion of capacitance & resistance measured in accumulation regime. Memory characteristics: C – V hysteresis loops with counter clockwise direction were obtained for different frequencies, having memory windows up to 4 V that are frequency independent, meaning that the memory effect is due to charge storage in SiGeSn NCs, NCs being obtained by RTA nanostructuring at temperatures of 520 and 530 oC.
(iii) Modelling of gate oxide / SiGeSn- oxide / tunnel oxide / p-Si substrate capacitor structures in Stage III / 2021, the oxide being HfO2 which is already a standard material in semiconductor processing in microelectronics: 3-layer capacitor was modelled with a complex equivalent RC circuit; electrical material parameters – resistivity ρ & dielectric constant κ of each component layer were evaluated; memory parameters – flatband voltage & stored carriers density were determined. The memory window (as the difference of flatband voltages corresponding to the C – V hysteresis branches) has high values from 3.1 V to 4 V for structures with floating gate of SiGeSn NCs storage nodes, and the stored carriers density reaches values on the order of 1013 electrons/cm2. So, the best results were obtained on gate HfO2 / floating gate of SiGeSn NCs embedded in HfO2 / tunnel HfO2 / p-Si substrate: 4 V memory window and 2×1013 electrons/cm2 stored carriers density. For structures with amorphous SiGeSn clusters (for RTA temperatures smaller than or equal to 500 oC), memory window is smaller, reaching the maxim value of 2.3 V, and the stored carriers density has values on the order of 1012 electrons/cm2, reaching the highest value of ~9×1012 electrons/cm2. The dielectric constants of each component layer were determined: κg = 15 – 16 for gate oxide, κf = 14 for floating gate, and κt = 19 – 20 for tunnel oxide. The layers resistivities are on the order of 10 MΩ×cm. The dielectric constants determined from simulation were used for calculating the stored carriers density.
Project web page https://infim.ro/en/project/sigesn-nanocrystals-with-charge-storage-properties-at-nanoscale-sigesnanomem/ was created & updated. 2 papers were published in Applied Surface Science and Nanotechnology, other 2 papers were submitted, being in reviewing stage at Acta Materialia and Scientific Reports, and other 2 papers are in writing stage, to be submitted to ISI-quoted journals (total of 6 papers – 5 papers being envisioned in Work Plan). 6 papers were presented at international conferences (3 planned): 1 invited, 1 oral, 4 posters.
In conclusion, the objectives & activities proposed in project “SiGeSn nanocrystals with charge storage properties at nanoscale” and results planned in Work Plan (Contract TE No. 19 /2018) were fully fulfilled.
Stage III / 2021 SUMMARY
In Stage III / 2021, the flatband voltage for each branch of C – V hysteresis and the memory window as the corresponding flatband voltage difference were determined. The flatband voltage was determined by 2 methods, namely by 1/C2 plot or by evaluating the voltage position at 80% of maximum capacitance. This was made for memory structures similar with structures M1 and M2 with intermediate layer of co-sputtered SiGeSn-HfO2, RTA annealed that were studied in Stage II / 2020. In Stage III / 2021, structures were RTA annealed at different temperatures and different times, on a large temperature range. For each kind of structure (M1/M2, RTA temperature and duration), C – V hysteresis loops were measured at different frequencies, and capacitance – frequency (C – f) and resistance − frequency (R – f) characteristics were recorded in accumulation regime. C – f and R – f curves were also simulated using an equivalent circuit model for the trilayer memory capacitor that consists in equivalent parallel RC circuit for each layer of the trilayer structure (gate oxide, floating gate, tunnel oxide, interfacial SiOx layer) and a series resistance (includes contacts and p-Si substrate resistances). Based on this model, the intrinsic material parameters of each component layer, i.e. dielectric constants and resistivity were evaluated. Also, the stored carriers density was calculated using the simulation results, i.e. the dielectric constants of gate oxide and floating gate and by considering the capacitor geometry (thicknesses of gate oxide and floating gate layers; SiGeSn NCs diameter). The stored carriers density was calculated in function of structures morphology (case 1: floating gate with amorphous SiGeSn clusters, the memory effect is due to electronic states present in clusters, being in fact Si-Ge-Sn related states – deep energy levels; case 2 – SiGeSn NCs act as charge storage node in the NC floating gate morphology). Electrical and memory parameters were evaluated considering the morphology. Thus, the structures with floating gate formed of SiGeSn NCs in HfO2 (gate HfO2 / SiGeSn NCs - HfO2 floating gate / tunnel HfO2 / p-Si substrate) have high memory windows up to 4 V, the stored carriers density reaching the value of 2.0×1013 electrons/cm2. Structures with amorphous SiGeSn show smaller memory windows, the highest value being 2.3 V; stored carriers density is on the order of 1012 electrons/cm2, reaching the maxim value of 8.9×1012 electrons/cm2. The obtained dielectric constants of each component layer are: 15 – 16 for gate oxide, 14 for floating gate, 19 – 20 for tunnel oxide; the resistivities are on the order of 10 M Ω×cm. The dielectric constants determined from simulation were used for calculating the stored carriers density. The values of dielectric constants obtained for HfO2 layers are in good agreement with literature.
The results together with the objectives and activities considered in the Work Plan for Stage III related to modelling of MOS capacitors with 3 layers HfO2 / SiGeSn - HfO2 / HfO2 / p-Si substrate and resulting parameters together with results dissemination (1 ISI paper submitted for publication) were fully fulfilled.
In Stage III / 2021, 2 papers were submitted for publication in ISI quoted journals, being in reviewing stage. Other 2 papers are in writing stage, to be submitted to ISI-quoted journals. We also participated with 2 papers at a prestigious conference in the field organized by APL Materials, namely Materials Challenges for Memory - MCFM 2021, virtual conference. The project web page https://infim.ro/en/project/sigesn-nanocrystals-with-charge-storage-properties-at-nanoscale-sigesnanomem/ was updated.
Stage II / 2020 SUMMARY
In Stage II / 2020, capacitor-like trilayer memory structures of gate HfO2 / SiGeSn NCs - HfO2 floating gate / tunnel HfO2 / p-Si substrate with floating gate formed of SiGeSn nanocrystals (NCs) acting as charge storage nodes, embedded in HfO2 were obtained and complexly characterized. The layers were deposited by magnetron sputtering deposition and subsequently nanostructured by rapid thermal annealing (RTA). Complex characterization of layers composition, morphology and structure was carried out by means of cross-section transmission electron microscopy (XTEM), Raman spectroscopy and X-ray diffraction (XRD). The electrical and memory properties of capacitors were investigated and correlated with the morphology and structure results.
Thus, in this stage we prepared different types of structures based on the Stage I / 2019 results, meaning that in Stage II / 2020, the technological parameters for structures preparation were refined, namely the SiGeSn-HfO2 intermediate layer composition (SiGeSn : HfO2 vol. ratio), the thicknesses of the 3 layers from the stack and the RTA temperature. For deposition, the gate HfO2 / SiGeSn - HfO2 / tunnel HfO2 / p-Si substrate configuration was chosen considering the best results from the first stage regarding the memory properties. 2 types of structures were deposited, one type M1 similarly with the one from the first stage and the second type M2 that has thicker intermediate and gate oxide layers and thinner tunnel oxide layer.
The XTEM investigations revealed the formation of SixGe1-x-ySny NCs in the floating gate, the NCs being rich in Ge, having very low Si content (x = 5% Si), diameters of ~ 5 nm and diamond crystalline structure (M1-RTA structures). 2 types of SixGe1-x-ySny NCs were evidenced in function of their position in the intermediate layer. First type NCs are practically of Ge (low content y ~ 2% Sn) and are positioned in the intermediate layer, while the second type of NCs are of GeSn with y ~ 15% Sn content and are positioned at the edge of intermediate layer. Raman spectroscopy showed also the formation of both GeSn NCs (y ~ 11 – 12% Sn, x = 5% Si) and Ge NCs in the M1 and M2 structures with RTA at 520 and 530 oC. It was shown that the annealing at 600 oC leads to the decrease of Sn content in the GeSn NCs due to the Sn diffusion to the surface. The GeSn NCs formation was also confirmed by XRD.
From the point of view of memory properties (correlated with the structure and morphology ones obtained from the complex characterization), in this stage, the best M1 and M2 structures are the ones RTA annealed at 520 and 530 oC. The SiGeSn NCs evidenced by XTEM, Raman and XRD measurements produce the counter clockwise C – V hysteresis with high memory window ΔV = 3 – 4 V as they act as charge storage nodes. The RTA annealing at higher temperatures (550 – 600 oC) leads to the deformation of hysteresis and decrease of its memory window to ~ 1 V.
The results together with the objectives and activities considered in the Work Plan for Stage II related to obtaining capacitor structures with NC SiGeSn-based floating gate and their complex characterization together with results dissemination (3 ISI papers; 2 papers presented at international conferences) were fully fulfilled.
In Stage II / 2020, 1 paper was accepted for publication in Applied Surface Science (and published - Applied Surface Science 542, 148702 (2021)) and 2 manuscripts are under finalization stage to be send to prestigious ISI-quoted journals. The project web page https://infim.ro/en/project/sigesn-nanocrystals-with-charge-storage-properties-at-nanoscale-sigesnanomem/ was updated and it is permanently updated.
Stage I / 2019 SUMMARY
In Stage I / 2019 we prepared trilayer memory capacitors of gate HfO2 / SiGeSn NCs - HfO2 floating gate / tunnel HfO2 / p-Si substrate in which the floating gate is formed of SiGeSn nanocrystals (NCs) acting as charge storage nodes, embedded in HfO2. The capacitors were prepared by magnetron sputtering and subsequently annealed by rapid thermal annealing for nanostructuring. Preliminary studies were carried out with the aim to optimize the technological conditions for obtaining structures with good memory properties.
Two types of structures were tested, i.e. M1 structures in which trilayers of gate HfO2 / SiGeSn / tunnel HfO2 were deposited on p-Si wafers and M2 structures with deposited trilayer configuration of gate HfO2 / SiGeSn-HfO2 / tunnel HfO2 on p-Si.
The formation of SiGeSn NCs in the floating gate was evidenced by X-ray diffraction (M1 structures). The capacitance-voltage characteristics measured on all structures (both M1 and M2 types) present counter-clockwise hysteresis loop with frequency-independent memory window demonstrating that the charge storage takes place only in SiGeSn NCs. The best memory characteristics were achieved on M2 structures, i.e. large memory window of 3.9 V.
In this stage, one article was published in Nanotechnology and 4 papers were presented at international conferences (ICASS – Italy, EMRS – France, IBWAP & EuroNanoForum – Romania). The project web page https://infim.ro/en/project/sigesn-nanocrystals-with-charge-storage-properties-at-nanoscale-sigesnanomem/ was created and updated.
Papers in ISI-quoted journals
- „SiGeSn quantum dots in HfO2 for floating gate memory capacitors”, C. Palade, A. Slav, O. Cojocaru, V.S. Teodorescu, T. Stoica, M.L. Ciurea, A.M. Lepadatu, Coatings 12, 348 (2022)
- „Nanoscale continuous transition from monoclinic to ferroelectric orthorhombic inside HfO2 nanocrystals stabilized by HfO2 capping and self-controlled Ge doping”, C. Palade, A.M. Lepadatu, A. Slav, O. Cojocaru, A. Iuga, V.A. Maraloiu, A. Moldovan, M. Dinescu, V.S. Teodorescu, T. Stoica, M.L. Ciurea, Journal of Materials Chemistry C 9, 12353 (2021)
- „Bandgap atomistic calculations on hydrogen-passivated GeSi nanocrystals”, O. Cojocaru, A.M. Lepadatu, G.A. Nemnes, T. Stoica, M.L. Ciurea, Scientific Reports 11, 13582 (2021)
- „Effects of Ge-related storage centers formation in Al2O3 enhancing the performance of floating gate memories”, I. Stavarache, O. Cojocaru, V.A. Maraloiu, V.S. Teodorescu, T. Stoica, M.L. Ciurea, Applied Surface Science 542, 148702 (2021)
- „Orthorhombic HfO2 with embedded Ge nanoparticles in nonvolatile memories used for the detection of ionizing radiation”, C. Palade, A. Slav, A.M. Lepadatu, I. Stavarache, I. Dascalescu, A.V. Maraloiu, C. Negrila, C. Logofatu, T. Stoica, V.S. Teodorescu, M.L. Ciurea, S. Lazanu, Nanotechnology 30, 445501 (2019)
- „Ferroelectric orthorhombic HfO2 phase formation in HfO2/Hf-HfO2/HfO2 3-layer stacks”, manuscript in writing stage, to be submitted to ISI-quoted journal
Papers at international conferences
- „Rapid thermal annealing temperature effects on charge storage behavior of SiGeSn quantum dots embedded in the high-k CMOS-compatible HfO2 in floating gate non-volatile memories”, C. Palade, A. Slav, O. Cojocaru, V.S. Teodorescu, T. Stoica, M.L. Ciurea, A.M. Lepadatu, 20th International Balkan Workshop on Applied Physics and Materials Science (IBWAP 2022), Constanta, July 12-15, 2022 (oral presentation)
- „SiGeSn quantum dots for non-volatile memories”, A.M. Lepadatu, C. Palade, I. Dascalescu, A. Slav, I. Stavarache, A.V. Maraloiu, V.S. Teodorescu, T. Stoica, M.L. Ciurea, EMRS 2021 Fall Meeting, virtual conference, September 20-23, 2021 (oral presentation)
- „Trilayer non-volatile memory structures with floating gate of SiGeSn nanocrystals embedded in HfO2”, C. Palade, A.M. Lepadatu, A. Slav, I. Stavarache, O. Cojocaru, V.A. Maraloiu, V.S. Teodorescu, T. Stoica, M.L. Ciurea, Materials Challenges for Memory - MCFM 2021, virtual conference, April 11-13, 2021, https://horizons.aip.org/materials-challenges/ (poster
- „Ferroelectric orthorhombic HfO2 phase in 3-layer memory structures of control HfO2 /floating gate of Ge nanoparticles in HfO2 /tunnel HfO2 on Si wafers”, C. Palade, A.M. Lepadatu, A. Slav, O. Cojocaru, A. Iuga, V.A. Maraloiu, A. Moldovan, M. Dinescu, V.S. Teodorescu, T. Stoica, M.L. Ciurea, MCFM 2021, April 11-13, 2021 (poster)
- „Advances in Ge nanocrystals-based structures for SWIR sensors and non-volatile memories”, C. Palade, A. Slav, A.M. Lepadatu, I. Stavarache, I. Dascalescu, O. Cojocaru, I. Lalau, S. Lazanu, C. Logofatu, T. Stoica, V.S. Teodorescu, M.L. Ciurea, 19th International Balkan Workshop on Applied Physics and Materials Science (IBWAP 2019), July 16-19, 2019, Constanta (invited presentation)
- „Germanium nanocrystals in oxide matrix for non-volatile memories and ionizing irradiation sensors”, M.L. Ciurea, I. Stavarache, A. Slav, C. Palade, A.-M. Lepadatu, I. Dascalescu, I. Lalau, O. Cojocaru, V.S. Teodorescu, A.V. Maraloiu, S. Lazanu, T. Stoica, 3rd International Conference on Applied Surface Science (ICASS 2019), June 17-20, 2019, Pisa (poster)
- „New advanced materials based on SiGeSn nanocrystals in oxides for SWIR phototodetectors and non-volatile memory devices”, C. Palade, I. Stavarache, A.M. Lepadatu, A. Slav, S. Lazanu, T. Stoica, V.S. Teodorescu, M.L. Ciurea, F. Comanescu, A. Dinescu, R. Muller, G. Stan, A. Enuica, M.T. Sultan, A. Manolescu, H.G. Svavarsson, EuroNanoForum 2019 (Nanotechnology and Advanced Materials Progress Under Horizon2020 and Beyond), June 12-14, 2019, Bucharest (poster)
- „GeSnSiO2 layers with embedded GeSn nanocrystals for sensing in SWIR”, A. Slav, C. Palade, C. Logofatu, I. Dascalescu, A.M. Lepadatu, I. Stavarache, S. Iftimie, V. Braic, S. Antohe, S. Lazanu, V.S. Teodorescu, D. Buca, M.L. Ciurea, T. Stoica, M. Braic, EMRS 2019 Spring Meeting, May 27-31, 2019, Nice (oral presentation)
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