Skip to main content
SpringerLink
Log in

Radiation-damage-induced defects in quartz. I. Single-crystal W-band EPR study of hole centers in an electron-irradiated quartz

  • Original Paper
  • Published:
Physics and Chemistry of Minerals Aims and scope Submit manuscript

Abstract

Single-crystal W-band electron paramagnetic resonance (EPR) spectra of an electron-irradiated quartz, measured at room temperature, 110 and 77 K, disclose three previously reported hole centers (#1, G and an ozonide radical). The W-band EPR spectra of these three centers clearly resolve six magnetically nonequivalent sites each, whereas previous X- and Q-band EPR studies reported Centers #1 and the ozonide radical to consist of only three symmetry-related components and interpreted them to reside on twofold symmetry axes in the quartz structure. The calculated g matrices of Center #1 and the ozonide radical show that deviations from twofold symmetry axes are <10°, which are probably attributable to distortion related to neighboring charge compensating ions. The W-band EPR spectra of Center G not only result in improved g matrices but also allow quantitative determination of the nuclear hyperfine (A) and quadrupole (P) matrices of its 27Al hyperfine structure that was incompletely resolved before. In particular, the g-maximum and g-minimum principal axes of Center G are approximately along two pairs of O–O edges of the SiO4 tetrahedron, while the unique A principal axis is approximately along a Si–Si direction. These new spin-Hamiltonian parameters suggest that Center G most likely involves trapping of a hole between two oxygen atoms related to a silicon vacancy and stabilized by an Al3+ ion in the neighboring tetrahedron (hence an O n−2 –Al3+ defect, where n is either 1 or 3).

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5

Similar content being viewed by others

References

  • Andrews L, Burkholder TR, Yustein JT (1992) Reactions of pulsed-laser evaporated aluminum atom with oxygen. Infrared spectra of the reaction products in solid argon. J Chem Phys 96:10182–10189

    Article  Google Scholar 

  • Archibong EF, St-Amant A (1998) The cyclic MO2 (M=Al, Ga) systems: CCSD(T) and DFT studies of their structures, harmonic vibrational frequencies and dissociation energies. Chem Phys Lett 284:331–338

    Article  Google Scholar 

  • Azzoni CB, Meinardi F, Paleari A (1994) Trapped-hole centers in neutron-irradiated synthetic quartz. Phys Rev B49:9182–9185

    Google Scholar 

  • Bednarek J, Schlick S (1991) Stability of radical intermediate in microscopically heterogeneous media. Photolysis of water adsorped on silica gel studied by ESR and DSC. J Phys Chem 95:9940–9944

    Article  Google Scholar 

  • Bershov LV, Marfunin AS, Speranskii AV (1978) The new stable electronic center in quartz. Izv Acad Nauk SSSR Ser Geol 1978(11):106–116 (in Russian)

    Google Scholar 

  • Bershov LV, Marfunin AS, Speranskii AV (1981) Types of radiation centers in vein quartz of some gold-bearing deposits. Geol Rud Mestor 23:80–86 (in Russian)

    Google Scholar 

  • Bershov LV, Martirosyan VO, Marfunin AS, et al (1971) The yttrium-stabilised electron-hole centers in anhydrite. Phys Stat Sol B44:505–512

    Google Scholar 

  • Bill H (1969) Investigation of colour centres in alcaline earth flourides. Helv Phys Acta 42:771–797

    Google Scholar 

  • Bossoli RB, Welsh TJ, Gilliam OR, et al (1979) Trapped-hole centers associated with trivalent cations in tetragonal GeO2. Phys Rev B19:4376–4381

    Google Scholar 

  • Botis SM, Nokhrin S, Pan Y, et al (2005) Natural radiation-induced damage in quartz. I. Correlations between cathodoluminescence colors and paramagnetic defects. Can Mineral 43:1565–1680

    Article  Google Scholar 

  • Botis SM, Pan Y, Bonli T, et al (2006) Natural radiation-induced damage in quartz. II. Distributions and implications for uranium mineralization in the Athabasca basin. Can Mineral 44:1569–1585

    Article  Google Scholar 

  • Botis SM, Pan Y, Nokhrin S, Nilges MJ (2007) Natural radiation-induced damage in quartz. III. A new ozonide center. Can Mineral (accepted with revision)

  • Carbonaro CM, Fiorentini V, Berardini F (2001) Proof of the thermodynamical stability of the E′ center in SiO2. Phys Rev Lett 86:3064–3067

    Article  Google Scholar 

  • Castner T, Känzig W (1957) The electronic structure of V-centers. J Chem Phys Solids 3:178–195

    Article  Google Scholar 

  • Clemmer DE, Dalleska NF, Armentrout PB (1992) Gas-phase thermochemistry of the group 3 dioxides: ScO2, YO2 and LaO2. Chem Phys Lett 190:259–265

    Article  Google Scholar 

  • Coronado JM, Maira AJ, Mathinez-Arias A, et al (2002) ESR study of the radicals formed upon UV irradiation of ceria-based photocatalysts. J Photochem Photobiol A: Chem 150:213–221

    Article  Google Scholar 

  • Cox RT (1976) ESR of an S=2 centre in amethyst quartz and its possible identification as the d4 ion Fe4+. J Phys C: Solid State Phys 9:3355–3361

    Article  Google Scholar 

  • Friebele EJ, Griscom DL, Stapelbroek M, et al (1979) Fundamental defect centers in glass: the peroxy radical in irradiated, high-purity, fused silica. Phys Rev Lett 42:1346–1349

    Article  Google Scholar 

  • Garrison EG, Rowlett RM, Cowan DL, et al (1981) ESR dating of ancient flints. Nature 290:44–45

    Article  Google Scholar 

  • Gonzales JM, King RA, Schaefer HF (2000) Analyses of the ScO− and ScO −2 photoelectron spectra. J Chem Phys 113:567–576

    Article  Google Scholar 

  • Götze J, Plötze M, Trautmann T (2005) Structure and luminescence characteristics of quartz from pegmatites. Am Mineral 90:13–21

    Article  Google Scholar 

  • Griscom DL, Friebele EJ (1981) Fundamental defect centers in glass: 29Si hyperfine structure of the non-bridging oxygen hole center and the peroxy radical in SiO2. Phys Rev B 24:4896–4898

    Article  Google Scholar 

  • Hochstrasser G, Antonini JF, Peyches I (1969) ESR of O −2 center on SiO2 surface. In: Somorjai CA (ed) The structure and chemistry of solid surfaces. Wiley, New York

    Google Scholar 

  • Howarth DF, Mombourquette MJ, Weil JA (1997) The magnetic properties of the oxygen-hole aluminum centres in crystalline SiO2. V. 17O-enirhced [AlO4/Li]+ and dynamics thereof. Can J Phys 75:99–115

    Article  Google Scholar 

  • Ikeya M (1993) New applications of electron paramagnetic resonance: ESR dating, dosimetry, and spectroscopy. World Scientific, Singapore

    Google Scholar 

  • Jani MG, Bossoli RB, Halliburton LE (1983) Further characterization of the E 1′ centre in crystalline SiO2. Phys Rev B 27:2285–2293

    Article  Google Scholar 

  • Jette AN, Gilbert TL, Das TP (1969) Theory of the self-trapped hole in the alkali halides. Phys Rev 184:884–894

    Article  Google Scholar 

  • Känzig W, Cohen MH (1959) Paramagnetic resonance of oxygen in alkali halides. Phys Rev Lett 3:509–511

    Article  Google Scholar 

  • Kappers LA, Gilliam OR, Stapelbroek M (1978) Points defects in particle-irradiated crystals of tetragonal GeO2. Phys Rev B17:4199–4206

    Google Scholar 

  • Lagendijk A, Glasbeek M, Van Voorst JDW (1973) Paramagnetic oxygen centres in SrTiO3 induced by light. Chem Phys Lett 20:92–95

    Article  Google Scholar 

  • Le Page Y, Calvert LD, Gabe EJ (1980) Parameter variation in low-quartz between 94 and 298K. J Phys Chem Solids 41:721–725

    Article  Google Scholar 

  • Lunsford JH (1973) ESR of adsorbed oxygen species. Cat Rev 8:135–156

    Article  Google Scholar 

  • Mackey JH, Boss JW, Wood DE (1970) EPR Study of substitutional–aluminum-related hole centers in synthetic α-quartz. J Magn Res 3:44–54

    Google Scholar 

  • Marfunin AS (1979) Spectroscopy, luminescence and radiation centers in minerals. Springer, Berlin

    Google Scholar 

  • Maschmeyer D, Lehmann G (1983) New hole centers in natural quartz. Phys Chem Miner 10:84–88

    Article  Google Scholar 

  • Mashkovtsev RI, Shcherbakova MYa, solntsev vp (1978) EPR of radiation hole centers in α-quartz. Tr Inst Geol Geofiz, Akad Nauk SSSR, Sib Otd 385:78–86 (in Russian)

    Google Scholar 

  • Mombourquette MJ, Weil JA (1986) Structure determination of the AlO4 hole centres in α-quartz by EPR and SCF MO. J Magn Res 66:105–117

    Google Scholar 

  • Mombourquette MJ, Weil JA, McGavin DG (1996) EPR-NMR Users’ manual. Department of Chemistry, University of Saskatchewan, Saskatoon, SK, Canada

    Google Scholar 

  • Morton JR, Preston KF (1978) Atomic parameters for paramagnetic resonance data. J Magn Res 30:577–582

    Google Scholar 

  • Murata C, Yoshida H, Kumagai J, Hattori T (2003) Active sites and active oxygen species for photocatalytic epoxidation of propene by molecular oxygen over TiO2-SiO2 binary oxides. J Phys Chem B107:4364–4373

    Google Scholar 

  • Nilges MJ, Smirnov AI, Clarkson RB, et al (1999) Electron paramagnetic resonance W band spectrometer with a low-noise amplifier. Appl Magn Reson 16:167–183

    Article  Google Scholar 

  • Ogoh K, Yamanaka C, Ikeya M, et al (1996) Two-center model for radiation induced aluminum hole center in stishovite. J Phys Chem Solids 57:85–88

    Article  Google Scholar 

  • Pak MV, Gordon MS (2003) Potential energy surfaces of Al+O2 reactions. J Chem Phys 118:4471–4476

    Article  Google Scholar 

  • Pan Y, Chen N, Weil JA, et al (2003) Electron paramagnetic resonance spectroscopic study of synthetic fluorapatite. Part III. Structural characterization of sub-ppm-level Gd and Mn in minerals at W-band frequency. Am Mineral 87:1333–1341

    Google Scholar 

  • Pan Y, Botis S, Nokhrin S (2006) Application of natural radiation-induced paramagnetic defects in quartz to exploration in sedimentary basins. J China U Geosci 17:258–271

    Article  Google Scholar 

  • Priest V, Cowan DL, Yasar H, et al (1991) ESR, optical absorption, and luminescence studies of the peroxy-radical defect in topaz. Phys Rev B44:9877–9882

    Google Scholar 

  • Purcell T, Weeks RA (1969) Radiation-induced paramagnetic states of some intrinsic defects in GeO2 glasses and crystals. Phys Chem Glasses 10:198–208

    Google Scholar 

  • Requardt A, Lehmann G (1985) An O 3−2 radiation defect in AlPO4 and GaPO4. J Phys Chem Solids 46:107–112

    Article  Google Scholar 

  • Rossman GR (1994) Colored varieties of the silica minerals. Rev Mineral 29:433–467

    Google Scholar 

  • Samoloivich MI, Tsinober LI, Kreiskop VN (1970) Features of smoky color of natural quartz crystals: morions. Sov Phys Crystallogr 15:438–440

    Google Scholar 

  • Schnadt R, Räuber A (1971) Motional effects in the trapped-hole center in smoky quartz. Solid State Commun 9:159–161

    Article  Google Scholar 

  • Schmidt MW, Baldridge KK, Boatz JA, et al (1993) General atomic and molecular electronic structure system. J Comput Chem 14:1347–1363

    Article  Google Scholar 

  • Schweizer S, Spaeth J-M (1999) New oxygen hole centers in the x-ray storage phosphor BaBrF. J Phys Condens Matter 11:1723–1733

    Article  Google Scholar 

  • Serebrennikov LV, Osin SB, Mal’tsev AA (1982) Infrared spectra of the products of reaction of aluminum, gallium, indium, and thallium with oxygen in an argon matrix. Estimation of the fundamentals, ν3, in cyclic superoxides of Group III metals. J Mol Struct 81:25–33

    Article  Google Scholar 

  • Solntsev VP, Shcherbakova MYa, Schastnev PV (1973) EPR study of structural defects in CaWO4. Zh Strukt Chim 14:222–229

    Google Scholar 

  • Walsby CJ, Lees NS, Claridge RFC, et al (2003) The magnetic properties of oxygen-hole aluminum centres in crystalline SiO2. VI: a stable AlO4/Li centre. Can J Phys 81:583–598

    Article  Google Scholar 

  • Wagner GR, Murphy J (1972) Paramagnetic hole centers in CeO2. Phys Rev B6:1638–1644

    Google Scholar 

  • Wang KM, Lunsford JH (1971) An electron paramagnetic resonance study of Y-type zeolites. III. O −2 on AlHY, ScY, and LaY Zeolites. J Phys Chem 76:1165–1168

    Google Scholar 

  • Weil JA (1984) A review of electron spin resonance and its applications to the study of paramagnetic defects in crystalline quartz. Phys Chem Miner 10:149–165

    Article  Google Scholar 

  • Zhao Q, Wang X, Cai T (2004) The study of surface properties of ZrO2. Appl Surf Sci 225:7–13

    Article  Google Scholar 

Download references

Acknowledgments

We wish to thank the Natural Science and Engineering Research Council (NSERC) of Canada for financial support of this study, and two reviewers and Dr. Milan Rieder for helpful comments and suggestions.

Author information

Authors and Affiliations

  1. Illinois EPR Research Center, University of Illinois at Urbana-Champaign, Urbana, IL, 61801, USA

    Mark J. Nilges

  2. Department of Geological Sciences, University of Saskatchewan, Saskatoon, SK, S7N 5E2, Canada

    Yuanming Pan

  3. Institute of Geology and Mineralogy, Siberian Branch of Russian Academy of Sciences, Novosibirsk, 630090, Russia

    Rudolf I. Mashkovtsev

Authors
  1. Mark J. Nilges
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Yuanming Pan
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Rudolf I. Mashkovtsev
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Yuanming Pan.

Rights and permissions

Reprints and permissions

About this article

Cite this article

Nilges, M.J., Pan, Y. & Mashkovtsev, R.I. Radiation-damage-induced defects in quartz. I. Single-crystal W-band EPR study of hole centers in an electron-irradiated quartz. Phys Chem Minerals 35, 103–115 (2008). https://doi.org/10.1007/s00269-007-0203-5

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s00269-007-0203-5

Keywords

Search

Navigation