TY - JOUR

T1 - Pulsed glow discharge enables direct mass spectrometric measurement of fluorine in crystal materials – Fluorine quantification and depth profiling in fluorine doped potassium titanyl phosphate

AU - Bodnar, Victoria

AU - Ganeev, Alexander

AU - Gubal, Anna

AU - Solovyev, Nikolay

AU - Glumov, Oleg

AU - Yakobson, Viktor

AU - Murin, Igor

N1 - Funding Information: The research has been supported by a grant from the Russian Science Foundation (grant No. 17-73-20089 ). The Authors are grateful to St. Petersburg State University Research Park (St. Petersburg State University, St. Petersburg, Russia): Interdisciplinary Resource Centers for Nanotechnology, Chemical Analysis and Materials and “Geomodel”, for providing access to their facilities.

PY - 2018/7

Y1 - 2018/7

N2 - A pulsed direct current glow discharge time-of-flight mass spectrometry (GD TOF MS) method for the quantification of fluorine in insoluble crystal materials with fluorine doped potassium titanyl phosphate (KTP) KTiOPO4:KF as an example has been proposed. The following parameters were optimized: repelling pulse delay, discharge duration, discharge voltage, and pressure in the discharge cell. Effective ionization of fluorine in the space between sampler and skimmer under short repelling pulse delay, related to the high-energy electron impact at the discharge front, has been demonstrated. A combination of instrumental and mathematical correction approaches was used to cope for the interferences of 38Ar2+ and 1H3 16O + on 19F+. To maintain surface conductivity in the dielectric KTP crystals and insure its effective sputtering in combined hollow cathode cell, silver suspension applied by the dip-coating method was employed. Fluorine quantification was performed using relative sensitivity factors. The analysis of a reference material and scanning electron microscope-energy dispersive X-ray spectroscopy was used for validation. Fluorine limit of detection by pulsed direct current GD TOF MS was 0.01 mass%. Real sample analysis showed that fluorine seems to be inhomogeneously distributed in the crystals. That is why depth profiling of F, K, O, and P was performed to evaluate the crystals' non-stoichiometry. The approaches designed allow for fluorine quantification in insoluble dielectric materials with minimal sample preparation and destructivity as well as performing depth profiling to assess crystal non-stoichiometry.

AB - A pulsed direct current glow discharge time-of-flight mass spectrometry (GD TOF MS) method for the quantification of fluorine in insoluble crystal materials with fluorine doped potassium titanyl phosphate (KTP) KTiOPO4:KF as an example has been proposed. The following parameters were optimized: repelling pulse delay, discharge duration, discharge voltage, and pressure in the discharge cell. Effective ionization of fluorine in the space between sampler and skimmer under short repelling pulse delay, related to the high-energy electron impact at the discharge front, has been demonstrated. A combination of instrumental and mathematical correction approaches was used to cope for the interferences of 38Ar2+ and 1H3 16O + on 19F+. To maintain surface conductivity in the dielectric KTP crystals and insure its effective sputtering in combined hollow cathode cell, silver suspension applied by the dip-coating method was employed. Fluorine quantification was performed using relative sensitivity factors. The analysis of a reference material and scanning electron microscope-energy dispersive X-ray spectroscopy was used for validation. Fluorine limit of detection by pulsed direct current GD TOF MS was 0.01 mass%. Real sample analysis showed that fluorine seems to be inhomogeneously distributed in the crystals. That is why depth profiling of F, K, O, and P was performed to evaluate the crystals' non-stoichiometry. The approaches designed allow for fluorine quantification in insoluble dielectric materials with minimal sample preparation and destructivity as well as performing depth profiling to assess crystal non-stoichiometry.

KW - FluorinePulsed glow dischargeTime-of-flight mass spectrometryPotassium titanyl phosphate (KTP)Nonlinear optical materials

KW - Fluorine

KW - Nonlinear optical materials

KW - Potassium titanyl phosphate (KTP)

KW - Pulsed glow discharge

KW - Time-of-flight mass spectrometry

KW - SECONDARY CATHODE

KW - LASER

KW - TIME

KW - KTIOPO4

KW - TRACE-ELEMENTS

KW - MOLECULAR ABSORPTION SPECTROMETRY

KW - NONLINEAR-OPTICAL PROPERTIES

KW - GROWTH

KW - SAMPLES

KW - EMISSION

UR - http://www.scopus.com/inward/record.url?scp=85045570283&partnerID=8YFLogxK

UR - http://www.mendeley.com/research/pulsed-glow-discharge-enables-direct-mass-spectrometric-measurement-fluorine-crystal-materials-fluor

U2 - https://doi.org/10.1016/j.sab.2018.04.002

DO - https://doi.org/10.1016/j.sab.2018.04.002

M3 - Article

AN - SCOPUS:85045570283

VL - 145

SP - 20

EP - 28

JO - SPECTROCHIMICA ACTA PART B-ATOMIC SPECTROSCOPY

JF - SPECTROCHIMICA ACTA PART B-ATOMIC SPECTROSCOPY

SN - 0584-8547

IS - 145

ER -