Iron-Ion Implantation into the Structure of Rock Crystal

A.V. Mukhametshin^a*, A.I. Gumarov^a**, I.V. Yanilkin^a***, I.R. Vakhitov^a****, V.I. Nuzhdin^b*****, F.G. Vagizov^a******, O.N. Lopatin^a*******, R.I. Khaibullin^b********, L.R. Tagirov^a********

^aKazan Federal University, Kazan, 420008 Russia

^bE.K. Zavoisky Physical–Technical Institute, Kazan Scientific Center, Russian Academy of Sciences, Kazan, 420008 Russia

E-mail: ^*adib.mv@gmail.com, ^**amir@gumarov.ru, ^***yanilkin-igor@yandex.ru, ^****ujay@mail.ru, ^*****nuzhdin@kfti.knc.ru, ^******vagizovf@gmail.com, ^*******Oleg.Lopatin@kpfu.ru, ^********rik@kfti.knc.ru, ^*********ltagirov@mail.ru

Received December 28, 2016

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Abstract

Iron ions with the energy of 40 keV have been implanted into colorless natural rock crystals to high fluencies of 1.0∙10¹⁷ and 1.5∙10¹⁷ ion/cm². These crystals were selected from Svetlinsky deposits of the Southern Urals, which are well-known as minerals with high quality and low content of impurities. A radical change in the color of the crystals after iron-ion implantation and subsequent high-temperature annealing in air has been revealed. The origin of color changes has been studied by using optical methods, as well as Mössbauer and X-ray photoelectron spectroscopy. It has been established that the high-dose and high-energy flow of ions results in the formation of various kinds of structural defects on the surface layer of the matrix, such as electron-hole centers, as well as in the formation at a specific depth of the irradiated matrix of the ultrafine iron-containing phases with a structure, which is non-coherent to the structure of the original matrix. The subsequent high-temperature annealing of the implanted quartz has changed the color of the samples to orange-yellow. This color is similar to the color of natural citrine. The orange color richness of the heat-treated samples grew with increasing amounts of embedded iron impurity in the crystal. The nature of orange-yellow coloration of the implanted and annealed quartz plates can be explained by the formation of ultrafine hematite nanoparticles located in a layer at a depth of ~15 nm. The possibility of refining the color of minerals by ion-beam exposure has been discussed.

Keywords: quartz, mountain crystal, citrine, ion implantation, Mössbauer spectroscopy, ornamental rocks

Acknowledgments. A.I. Gumarov, I.V. Yanilkin, I.R. Vakhitov, L.R. Tagirov, and F.G. Vagizov are grateful for the support of the investigation by the subsidy allocated to Kazan Federal University as part of the state program for increasing its competitiveness among the world's leading centers of science and education.

The plates were analyzed by the method of X-ray photoelectron spectroscopy using equipment of the Center of Shared Facilities for Physical and Chemical Research of Substances and Materials, Kazan Federal University.

Figure Captions

Fig. 1. The crystal structure of quartz.

Fig. 2. The optical absorption spectra of quartz plates: initial colorless and transparent plate, after the implantation of iron ions to fluencies of of 1.510¹⁷ ion/cm²; the same implanted plate after subsequent annealing in the air at the temperature of 950 ?C for 60 min.

Fig. 3. The Mössbauer spectra of conversion electrons in the quartz plates: (а) implanted with iron ions to fluencies of 1.510¹⁷ ion/cm²; (b) implanted with iron ions to fluencies of 1∙10¹⁷ ions/cm² and then subsequently annealed in the air at the temperature of 950 ?C for 60 min.

Fig. 4. The depth profiles of concentrations for Fe, Si, O, and C in the quartz plate implanted with iron ions to fluencies of 1.510¹⁷ ion/cm². The solid line shows the maximum of concentration in the depth profile for iron (Fe_max).

Fig. 5. XPS Fe 2p lines recorded at different depths in the range of 2–80 nm from sample surface for the quartz plate implanted with iron ions to fluencies of 1.510¹⁷ ion/cm² (left panel) and then thermally annealed in the air (right panel).

Fig. 6. XPS O 1s lines recorded at the depth of 16 nm for the quartz plate implanted with iron ions to fluencies of 1.510¹⁷ ion/cm² (curve 1) and then annealed in the air at the temperature of 950 ?C for 60 min (curve 2).

Photo 1. The faceted rock crystal (rhinestone).

Photo 2. The same rhinestone after iron implantation and high-temperature annealing in the air.

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For citation: Mukhametshin A.V., Gumarov A.I., Yanilkin I.V., Vakhitov I.R., Nuzhdin V.I., Vagizov F.G., Lopatin O.N., Khaibullin R.I., Tagirov L.R. Iron-ion implantation into the structure of rock crystal. Uchenye Zapiski Kazanskogo Universiteta. Seriya Estestvennye Nauki, 2017, vol. 159, no. 1, pp. 5–20. (In Russian)

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