This LTP-NASICONreadme.txt file was generated on 20250313 by Daniela R. Fontecha ------------------- GENERAL INFORMATION ------------------- 1. Title of Dataset: Nanoscale Mixed Ion-Electron Conducting NASICON-type Thin-Films: Lithium Titanium Phosphate via Atomic Layer Deposition 2. Author Information: drfontec@umd.edu Principal Investigator Contact Information: Name: Keith E. Gregorczyk Institution: University of Maryland Address: 8279 Paint Branch Dr, College Park, MD 20740 Email: kgregorc@umd.edu Associate or Co-investigator Contact Information: Name: Daniela R. Fontecha Institution: University of Maryland Address: 8279 Paint Branch Dr, College Park, MD 20740 Email: drfontec@umd.edu 3. Date of data collection: <20230701> to <20240601> 4. Geographic location of data collection: University of Maryland 5. Information about funding sources that supported the collection of the data: This work was supported by Murata Integrated Passive Solutions, the U.S. Department of Energy, and the National Science Foundation. Murata supported the evaluation and testing of ALD solid electrolyte materials for application in 3D solid state capacitor structures. Under the Office of Science, Office of Basic Energy Sciences, Grant DE-SC0021070, DOE supported the synthesis of Li-containing titanium phosphates with composition varied through a dopant-supercycle process. A.T.H. and J.C. acknowledge support from the Center for Enhanced Nanofluidic Transport (CENT), an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences, under Award # DE-SC0019112. D.R.F was supported by the National Science Foundation Graduate Research Fellowship Program under Grant No. DGE 1840340. Any opinions, findings, and conclusions or recommendations expressed in this material are those of the author(s) and do not necessarily reflect the views of the National Science Foundation. -------------------------- SHARING/ACCESS INFORMATION -------------------------- Recommended citation for the data: Daniela R. FontechaDaniela R. Fontecha, Alexander C. Kozen, David M. Stewart, Alex T. Hall, John Cumings, Gary W. Rubloff, Keith E. Gregorczyk. (2025). Nanoscale Mixed Ion-Electron Conducting NASICON-type Thin-Films: Lithium Titanium Phosphate via Atomic Layer Deposition. Location: ACS Applied Materials and Interfaces> --------------------- DATA & FILE OVERVIEW --------------------- 1. File List: A. Filename: 1-2_XPS_LTP7_850C_3hrs_quench_high resolution_ C 1s, 1-2_XPS_LTP7_850C_3hrs_quench_high resolution_ O 1s, 1-2_XPS_LTP7_850C_3hrs_quench_high resolution_ P 2p, 1-2_XPS_LTP7_850C_3hrs_quench_high resolution_ Ti 2p, 1-2_XPS_LTP7_850C_3hrs_quench_high resolution_Li 1s, 1-2_XPS_LTP7_850C_3hrs_quench_survey scan, 1-2_XPS_LTP7_as-deposited_high resolution_C 1s, 1-2_XPS_LTP7_as-deposited_high resolution_Li 1s, 1-2_XPS_LTP7_as-deposited_high resolution_P 2p, 1-2_XPS_LTP7_as-deposited_high resolution_Ti 2p, 1-2_XPS_TiPO_as-deposited_high resolution_C 1s, 1-2_XPS_TiPO_as-deposited_high resolution_O 1s, 1-2_XPS_TiPO_as-deposited_high resolution_P 2p, 1-2_XPS_TiPO_as-deposited_high resolution_Ti 2p, 1-2_XPS_TiPO_as-deposited_survey scan, 1-2-4_XPS_LTP7_as-deposited_high resolution_O 1s, 1-2-4_XPS_LTP7_as-deposited_survey scan File name structure: [figure # (#-#)] [technique] [sample name] [annealing temp] [annealing time] [annealing type (quench/ramp)] [resolution (high resolution or survey spectrum)] [region name] Short description: Figure 1 and 2; X-ray photoelectron spectroscopy (XPS) of titanium phosphate (TiPO) as-deposited, LTP7 annealed at 850C for 3 hrs, and LTP as-deposited raw data files B. Filename: 3_Raman_LTP7_850C_10hrs_quench, 3_Raman_LTP7_850C_10hrs_ramp, 3_XRD_LTP7_850C_3hrs_quench File name structure: [figure # (#-#)] [technique] [sample name] [annealing temp] [annealing time] [annealing type (quench/ramp)] Short description: Figure 3; Raman spectroscopy of LTP7 samples annealed at 850C for 10 hrs with and without a quench step. X-ray diffractometry (XRD) of LTP7 samples annealed at 850C for 3 hours with a quench step. C. Filename: 4_Raman_LTP1_center_850C_30min_quench, 4_Raman_LTP1_edge_850C_30min_quench, 4_Raman_LTP7_center_650C_10hr_ramp, 4_Raman_LTP7_center_850C_30min_quench, 4_Raman_LTP7_edge_650C_10hr_ramp, 4_Raman_LTP7_edge_850C_30min_quench, 4_Raman_LTP7_inner ring_650C_10hr_ramp File name structure: [figure # (#-#)] [technique] [sample name] [annealing temp] [annealing time] [annealing type (quench/ramp)] Short description: Figure 4; Raman spectroscopy taken at different spots on the film of LTP7 samples annealed at 850C and 650C. D. Filename: 4_XPS_LTP7_center_650C_10hrs_ramp_high resolution_O 1s, 4_XPS_LTP7_center_650C_10hrs_ramp_survey scan, 4_XPS_LTP7_edge_650C_10hrs_ramp_high resolution_ O 1s, 4_XPS_LTP7_edge_650C_10hrs_ramp_survey scan, 4_XPS_LTP7_inner ring_650C_10hrs_ramp_high resolution_O 1s, 4_XPS_LTP7_inner ring_650C_10hrs_ramp_survey scan File name structure: [figure # (#-#)] [technique] [sample name] [annealing temp] [annealing time] [annealing type (quench/ramp)] [resolution (high resolution or survey spectrum)] [region name] Short description: Figure 4; X-ray photoelectron spectroscopy (XPS) taken at different spots on the film of LTP7 samples annealed at 650C for 10 hours. E. Filename: 5_Raman_anatase TiO2_650C_10 hr_ramp, 5_Raman_LTP2_650C_1hr_quench, 5_Raman_LTP7_650C_1hr_quench, 5_Raman_LTP7_850C_1hr_quench File name structure: [figure # (#-#)] [technique] [sample name] [annealing temp] [annealing time] [annealing type (quench/ramp)] Short description: Figure 5; Raman spectroscopy of LTP7 and LTP2 samples annealed at 650C and 850C. F. Filename: 6_SAED_LTP2_650C_9min_quench_LTP particle, 6_SAED_LTP2_650C_9min_quench_TiO2 particle, 6_TEM_LTP2_650C_9min_quench_LTP particle, 6_TEM_LTP2_650C_9min_quench_TiO2 particle, 6_TEM_x-section_LTP2_650C_9min_quench File name structure: [figure # (#-#)] [technique] [sample name] [annealing temp] [annealing time] [annealing type (quench/ramp)] [particle imaged] file extension: .tif Short description: Figure 6; Selected area electron diffraction (SAED) and transmission electron microscopy (TEM) of LTP2 sample annealed at 650C for 9 min. G. Filename: 7_EIS_LTP2_650C_9min_25C, 7_EIS_LTP2_650C_9min_60C, 7_EIS_LTP2_650C_9min_80C, 7_EIS_LTP2_650C_9min_100C, 7_EIS_LTP2_Fitting Parameters File name structure: [figure # (#-#)] [technique] [sample name] [annealing temp] [annealing time] [annealing type (quench/ramp)] [measurement temperature] Short description: Figure 7; electrochemical impedance spectroscopy (EIS) of LTP2 metal-insulator-metal stack annealed at 650C for 9 min. Fitting parameters displayed in the indicated file. H. Filename: 7_EIS_LTP2_650C_9min_25C, 7_EIS_LTP2_650C_9min_60C, 7_EIS_LTP2_650C_9min_80C, 7_EIS_LTP2_650C_9min_100C File name structure: [figure # (#-#)] [technique] [sample name] [annealing temp] [annealing time] [annealing type (quench/ramp)] [measurement temperature] extension: .mpr Short description: Same content as [G] but can be opened in EC-Lab software I. Filename: S1_Raman_LTP2_650C_9min_quench, S1_Raman_LTP7_650C_9min_quench, S1_Raman_LTP7_as-deposited File name structure: [figure # (#-#)] [technique] [sample name] [annealing temp] [annealing time] [annealing type (quench/ramp)] Short description: Figure S1; Raman spectroscopy of LTP7 as-deposited, annealed at 650C 9 min, and LTP2 annealed at 650C 9 min. J. Filename: S4_XRD_LTP2_650C_9min_quench File name structure: [figure # (#-#)] [technique] [sample name] [annealing temp] [annealing time] [annealing type (quench/ramp)] Short description: X-ray diffractometry (XRD) of LTP2 samples annealed at 650C 9 min K. Filename: S5_CA_LTP2_650C_9min_quench_50mV, S5_CA_LTP2_650C_9min_quench_100mV, S5_CA_LTP2_650C_9min_quench_350mV, S5_CA_LTP2_650C_9min_quench_500mV File name structure: [figure # (#-#)] [technique] [sample name] [annealing temp] [annealing time] [annealing type (quench/ramp)] [applied voltage] Short description: Figure S5; chronoamperometry (CA) of LTP2 samples annealed at 650C 9 min I. Filename: S7_SEM_LTP2_650C_9min_quench_cross-section, S7_SEM_LTP2_650C_9min_quench_planar, S7_SEM_LTP7_850C_3hr_quench_cross-section, S7_SEM_LTP7_850C_3hr_quench_planar File name structure: [figure # (#-#)] [technique] [sample name] [annealing temp] [annealing time] [annealing type (quench/ramp)] [orientation] file extention: .jpg, .tif Short description: Figure S7; scanning electron microscopy (SEM) of LTP2 and LTP7 annealed samples. I. Filename: XPS Processed Data file extention: .sff and .vms Short description: .vms file of all of the processed XPS data can be viewed in CASA XPS software. 2. Relationship between files: Files are separated by figure in the final manuscript and technique. Unless otherwise indicated, all files are .txt files. -------------------------- METHODOLOGICAL INFORMATION -------------------------- 1. Description of methods used for collection/generation of data: ALD Process Development. Test-grade wafers (University Wafer) were pumped down to 10-7 Torr in a load-lock chamber before transferring them into the ALD reactor. Depositions were conducted at 300 oC in a Cambridge Nanotech (now Veeco) Fiji F200 Gen 1 ALD reactor coupled to an ultra-high vacuum (UHV) cluster system (<10-8 Torr). ALD precursors were lithium tert-butoxide (LiOtBu) (Sigma, 97%), deionized water, trimethylphosphate (TMP) (Sigma, 99%), and titanium (IV) isopropoxide (TTIP) (Sigma, 99.99 %) with argon (Airgas UHP, 99.999%) used as the carrier gas. The base pressure of the ALD reactor was 1x10-6 Torr, and the process pressure was maintained at 200 mTorr by flow of UHP argon (Airgas, 99.999%) gas. LiOtBu was kept at 150 oC in a stainless-steel bubbler and delivered to the ALD reactor with 40 sccm argon carrier gas flow. H2O was kept at room temperature, TMP was kept at 70 oC, and TTIP was kept at 100 oC. H2O, TMP, and TTIP were all kept in stainless-steel vapor draw cylinders. ALD films were deposited with lithium oxide and titanium phosphate subprocesses. The lithium oxide subprocess consisted of a 5 second LiOtBu pulse, and a 0.06 second H2O pulse. The titanium phosphate subprocess consists of a 0.2 second TMP pulse followed by a 0.06 second water pulse and a 0.1 second TTIP pulse followed by a 0.06 second water pulse. All processes have 20 second Ar purge after each precursor pulse. Real-time in-situ monitoring of film thickness was performed using a J.A Woollam M-2000D spectroscopic ellipsometer with a spectral range of 193-1000 nm. Film thicknesses were fit to an optical Cauchy model and the measurements then verified by cross-sectional scanning electron spectroscopy (SEM). Sample Preparation. X-ray photoelectron spectroscopy (XPS) and X-ray diffractometry (XRD) were performed on films deposited on bare p-doped Si(100) test-grade wafers (University Wafer) with resistivity of 1-100 ohm-cm because Si does not interfere with the measurements in this case. Raman spectroscopy and electrochemical impedance spectroscopy (EIS) were performed on films deposited on Si chips with 500 nm thermal SiO2, 10 nm Ti, and 100 nm Pt (i.e. Si/SiO2/Ti/Pt stack). Annealing procedures. For Raman, XRD, and XPS, films were annealed at various times and temperatures in a tube furnace under a flowing N2 environment. Some films were allowed to radiatively cool and others were quenched to room temperature on a metal table acting as a heat sink. For impedance measurements, films were annealed in the rapid thermal annealer (RTA) at 650 oC for 8.5 minutes under a flowing N2 atmosphere and subsequently quenched to room temperature. X-Ray Photoelectron Spectroscopy (XPS). Post-deposition, films were transferred under UHV to a Kratos Ultra DLD Surface Analysis system (1x10-9 Torr) for XPS analysis. XPS data were collected using a monochromatic Al Kα (1486 eV) X-ray source at 15 kV and a total anode power of 150 W. Survey spectra were collected with a pass energy of 160 eV and binding energy step size of 1 eV. High resolution spectra were collected with a pass energy of 20 eV and a binding energy step size of 0.1 eV at the appropriate number of scans to produce a satisfactory signal/noise ratio. Casa XPS was used to analyze all data. XPS peaks were fit using a Shirley background and 30/70 Gaussian/Lorentzian pseudo-Voigt functions. Elemental quantification was done by comparing the ratios of high-resolution peak areas with the tabulated Kratos relative sensitivity factors. All spectra were charge calibrated to the C 1s peak at 284.8 eV. X-Ray Diffraction (XRD). XRD was performed by a PANalytical XPert Pro MRD system in a grazing-incidence (GI)-XRD configuration with a scan rate of 0.025 o/s and step size of 0.05 o. Cu-Kα (λ = 1.54 Å) radiation source was used. The diffraction patterns were compared with primary references from the International Center for Diffraction Data (ICDD) for identification. Rietveld Refinement was performed using Profex. Raman Spectroscopy. Measurements were recorded in air with a “Labram HR” microscope system (Horiba Jobin Yvon USA). A 633 nm laser (HeNe) with a D1 intensity filter was used. The incident laser power was controlled to 1 mW and ~2µm diameter spot size with a 100x microscope objective. A 600 gr/mm grating was used for acquisitions with 20s exposure and 5 repetitions. Microscopy. Scanning electron microscopy (SEM) and focused ion beam (FIB) cross-sections were performed on a dual-beam field emission SEM/FIB system (Tescan, XEIA3) with a 10 kV acceleration voltage. Transmission electron microscopy (TEM) imaging was performed using a JEOL JEM-2100F operated at 200 kV. All images were formed on a Gatan OneView CMOS camera. Sample preparation: TEM cross-sections were prepared by hand polishing using a PELCO Tripod Polisher followed by final thinning in a Gatan PIPS II ion polisher. Impedance Measurements. Electrochemical impedance spectroscopy (EIS) was performed with a Biologic VSP potentiostat in an argon-filled glovebox (MBraun) maintained at <0.5 ppm H2O and O2. Finished devices were placed on a custom-built mica glass-ceramic stage with a proportional integral-derivative (PID) temperature controller. Electrical contact was made with micromanipulator probes. EIS measurements were made at temperatures between 25 and 100 oC at frequencies of 200 kHz to 250 mHz with an AC amplitude of 20 mV. DC relaxation was performed by applying a series of DC voltages (50, 100, 350, 500 mV) for 10 minutes each. Sample Preparation: LTP was deposited on Si/SiO2/Ti/Pt stacks. The Pt layer serves as the bottom contact for the metal-insulator-metal stacks. Once LTP is deposited, the chips were annealed in the rapid thermal annealer (RTA) at 650 oC for 8.5 minutes under a flowing N2 atmosphere. Post-anneal, a stainless-steel shadow mask with circular holes 400 um in diameter was placed above the LTP layer to pattern a top current collector of Au, forming a vertical Pt/LTP/Au stack for impedance testing. A 120 nm Au top-contact was deposited on the samples without air-exposure using a resistive metal evaporator integrated with the UHV cluster system. 2. Instrument- or software-specific information needed to interpret the data: Software used to interpret EIS data: EC Lab Software used to interpret XPS data: CASA XPS However, both types of data sets are also offered in .txt format. ----------------------------------------- DATA-SPECIFIC INFORMATION FOR: [Any XPS high resolution spectra files] ----------------------------------------- 1. Number of variables: Raw data is the binding energy (BE) and counts (CPS) columns. The rest of the columns vary by sample and region name. 3. Variable List A. Name: [BE] Description: [binding energy measured in eV] B. Name: [CPS] Description: [number of counts] B. Name: [region name (i.e., Ti 2p, Li 1s, P 2p, O 1s, or C 1s)] Description: [Counts for individual component in the indicated region from the fit after data analysis in CASA XPS] C. Name: [envelope] Description: [the sum of all of the regions in B]