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High Pressure Research: An International Journal

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Ruby-spheres as pressure gauge for optically transparent high pressure cells

J. C. Chervin , B. Canny & M. Mancinelli
a a a b

Laboratoire de Physique des Milieux Condenss, UMR 7602, Universit Pierre et Marie Curie, B77, 4, Place Jlissieii, Paris, 75252, France
b

R.S.A. Le RUBIS SA, RN 85-BP 16, Jarrie, 38560, France Version of record first published: 19 Aug 2006.

To cite this article: J. C. Chervin, B. Canny & M. Mancinelli (2001): Ruby-spheres as pressure gauge for optically transparent high pressure cells, High Pressure Research: An International Journal, 21:6, 305-314 To link to this article: http://dx.doi.org/10.1080/08957950108202589

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High Prxtmwe Researrh. 2001, Vol. 21, pp. 305-314 Reprints available directly from the publisher Photocopying permitted by license only

2001 OPA (Overseas Publishers Association) N.V Published by license under the Gordon and Breach Science Publishers imprint, a member of the Taylor & Francis Group.

RUBY-SPHERES AS PRESSURE GAUGE FOR OPTICALLY TRANSPARENT HIGH PRESSURE CELLS

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J. C. CHERVIN", B. CANNY* and M. MANCINELLIb

aLaboratoire de Physique des Milieux CondensPs, UMR 7602, Universitk Pierre et Marie Curie, B77, 4, Place Jlissieii, 75252 Paris, France; bR.S.A. Le RUBIS SA, - RN 85 - BP 16, 38560 Jarrie, France
(Received January 12. 2002; Revised February 17, 2002; In j n a l form February IS, 2002)

Ruby is widely used as an in siru pressure gauge for optically transparent pressure cells up to the megabar range. Usually ruby chips cut from bulk crystals are used which are ill-characterized and inconvenient to handle and to identify visually. Here we present a systematic study on corundum samples doped with C 2 ions with concentration from 60 to 23500 ppm to determine the optimal conditions for the use as an accurate pressure marker. The influence of the excitation wavelength on the luminescence spectra was investigated. These studies led to the synthesis of small (1-50 micrometer) ruby spheres with 3000 ppm chromium concentration. After annealing and a heat treatment to avoid internal strains we find reproducible values of the position and the width of the fluorescence lines. These ruby spheres are not only well suited for a reliable and accurate pressure determination in experiments using diamond anvil cells, but can also be used as an in sihr micro-thermometer in high pressure-low temperature studies.
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Keywords: DAC; high pressure; ruby gauge

INTRODUCTION
Optically transparent pressure cells, and particularly diamond anvil cells allow a variety of measurements under high static pressures to beyond 1 Mbar (100 GPa) [ 1,2]. In this technique, the pressure in the experimental volume is generally measured using a gauge based on the secondary scale of ruby (A1203:Cr3 ). The pressure dependence of the photo luminescent emission was determined previously as a function of temperature [3] and pressure [4]. A calibration of the ruby scale at low temperature was performed up to 1.2 GPa [5]. However, the ruby scale calibration depends to a certain extent
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* Corresponding author. Fax: 33-1-4427 4469; E-mail: bc@pmc.jussieu.fr

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also on the growth conditions of the samples [6], the chromium concentration [7] and also the nature of the light excitation [S]. Some discrepancies occur when recording spectra of crystals from different sources, and it appears necessary to obtain convenient and well-characterized high-quality samples with homogenous and reproducible luminescence characteristics. This is the purpose of this short report. The Ruby Luminescence
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Aluminum oxide, so-called corundum or sapphire, doped with the trivalent chromium, is well known by mineralogist as ruby. Depending on the C f + concentration, pink, standard and dark red rubies are obtained. The optical properties of ruby were widely studied in the 1950s, as it was used for the first solid laser material. Corundum is rhombohedra1(space group D3,,) with two formula units per unit cell. The A13+ ion is at the C3-axis close to the center of a distorted octahedron and the six oxygen ions at its vortices, placed in two parallel planes [9]. When Cr3+ is replaced by A13+ which has a smaller ionic radius, additional trigonal or tetragonal distortions occur. Following Sugano and Tanabe [lo], the fimdamental level 4F of the free Cr3+ ion, whose symmetry becomes 4A2 in the crystalline field, is split by 0.02nm in two sub-levels, the zero field splitting [l 11, which can be observed at very low (<4K) temperature. Luminescence is emitted from an excited doublet *E It consists mainly of the two well-known R1 and R2 lines with respective wavelengths at 694.25 nm and 692.74nm (at 300K) [12,13]. The FWHM of the R1 line at room temperature is around 0.53nm and refines down to 0.05 nm at liquid helium temperature. Apart from the temperature dependence, the line width depends on different other parameters, particularly on the chromium concentration [7], and also on homogeneity in the chromium distribution of the crystal. For large chromium concentrations (beyond 6000 ppm) interactions between ions can be observed which lead to new lines in the luminescent spectra, mainly the NI/N2 doublet at 704.0 and 700.9 nm (at lOK). At very high pressure these lines are more intense than the R lines, which can lead to conhsion and errors in the pressure determination [14,15].

EXPERIMENTAL Influence of the Cr3+ Concentration Ten ruby samples from slightly pink to dark red were synthesized by the French R.S.A. Le Rubis company [16]. The nominal concentrations

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(Cr3+/A13+ ratio) determined in the initial mixture varied from 60ppm to 23500ppm. However, analyses by atomic absorption and by a microprobe (model micro-Camebax SX50) showed that the real concentration of chromium in the samples was -50% lower. Crystals were cut in slabs of 100 itm thickness and used in the following experiments. Luminescence spectra were recorded on a triple monochromator T-800 Coderg equipped with a photon counting detector. The resolution of this setup was 0.01 nm when slits of 40 pm were used. A krypton laser Coherent 3000K provided the excitation source which was adjusted to 1 mW at a given wavelength. Each sample was successively excited by the blue (419.1 nm), green (530.8 nm) and red (647.1 nm) krypton lines. Measurements were made at room temperature and also at variable temperature, from 4.2 K to 300 K. Figure 1 shows the variation of the intensity of the R-lines as a function of the chromium concentration on a semi-logarithmic plot for two exciting wavelengths, 419.1 nm and 530.8nm, at 300K. Measurements with the red laser line at 647.1 nm did not give significant information, the luminescence being very weak in that case. A concentration of 5000ppm Cr3+ gave a maximal intensity in both cases. The frequency and the FWHM of the R lines were also studied at room temperature as a function of different excitation light power. It was found that the variation of the R, and R2 line frequencies is not significant when the power remains lower than 100 mW. For larger powers, a shift of 0.1 nm of the whole spectrum can be observed, no doubt due to local heating of the sample. Similarly the FWHM of the R, line remains at 0.55 nm for low power levels but increases to 0.65 nm for powers larger than 10mW. Figure 2 presents the evolution of the FWHM of R, and R2 at the same conditions as those in Figure 1. For R,, the width (FWHM) varies from 0.50f0.02nm for low chromium concentrations and up to 0.84 f0.02 nm for the highest concentration. At 3000ppm, the FWHM is around 0.55 and 0.58nm, which is close to the intrinsic line width at this temperature. This value of the Cr3+ concentration appears to be an acceptable compromise between line width and intensity for the use of ruby as pressure marker.
Ruby Spheres

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The R.S.A. Le Rubis Company synthesized ruby spheres with an effective Cr3+ concentration in the range 3000-4000 ppm. The diameter of the spheres varies from 1 pm to 50 pin (see Fig. 3). Compared to ruby samples in form of chips, such ruby spheres have the considerable advantage that they can be easily identified and distinguished from other samples in the experimental

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volume. Such as grown ruby spheres presented very inhomogeneous luminescent spectra. They are mainly in the corundum y phase which is opaque. It was obvious that the samples should be annealed to transform them to the transparent a phase and to eliminate the internal strains. The samples are placed in a crucible and heated in a standard furnace in air. The temperature was increased at a constant rate to 1500 C within 3 days, maintained under these conditions for one week, and then decreased to 300K at a rate of 70 K per day. After this heat treatment, arbitrarily chosen samples exhibited a FWHM of 0.55 f0.02 nm with good reproducibility. After temperature cycles with a maximum temperature lower than 1500 C, or after rapid cooling from this temperature, we found a large amount of non-transparent spheres as well as a substantially larger dispersion on the observed line widths.

Ruby as a Micro-Thermometer
Optical transparent pressure cells are often able to operate at variable temperature, in particular membrane diamond anvil cells (MDAC). The design developed in our laboratory [17], for example, can be easily placed in a vacuum chamber and used experiments from 4 to 800K. The pressure is monitored from outside. In such a set-up, the ruby spheres may also be used as a micro-thermometer. The variation of the ruby luminescence under variable temperature is well known, particularly at low temperature [7]. For our ruby spheres, a polynomial fit to the R1line position was made in the range 108 K-300 K; below -108 K, the wavelength of the R1 line remains essentially constant (see Fig. 4). The best fit gave the following relation: A(nm) = 693.4 - O.O22(T - 108)

+ 1.310-5(T -

where A is the R1 wavelength in nanometer at ambient pressure as a function of temperature in Kelvin. For temperatures below 100 K, Weinstein showed that the respective population of the emitting levels allows to determine the temperature through the relation [ 181:

where 1, and I2 are respectively the intensities of the R, and R2lines. For the ruby spheres with 3000 ppm Cr3+ concentration, the coefficients were deter-

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mined to be A = 41.86 K and q = 0.625 which gives a precision of -1 K in the range 10-100K. [19]. For temperatures above 100 K, both pressure and temperature can be determined in sitii by the two calibrants technique. The luminescent compound SrB407 doped with Sm2+ [20] is a favorite candidate for use as a second calibrant. Since the Sm2 luminescent lines are quasi insensitive to temperature, it is possible to determine the pressure and the temperature simultaneously when a ruby and a SrB407:Sm2+ sample are placed in the highpressure chamber. This technique was previously proposed by F. Datchi et al. [21]. For temperatures above 750K, it was shown that no reliable data can be obtained, due to the broadening of the luminescent lines, the decrease of the intensity and the increase of the background [22].
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CONCLUSION
Ruby samples should be carefully chosen for accurate and reliable pressure measurements. We have investigated some of the luminescence properties of ruby (frequency, width and intensity of the R-lines) as a function of C 2 + concentration. A concentration of 3000 ppm chromium seems to be optimal for use in high-pressure experiments. Small ruby spheres of 1 to 50 pm with this C?+ content where synthesized which (after annealing) were shown to be convenient pressure markers for in situ pressure measurements in DAC cells. The temperature dependence of the R-lines allows these ruby spheres also to be used as an in situ thermometer.

Acknowledgenients

This work was initiated by J. M. Besson and supported in part by the French Bureau National de MCtrologie under contract nr. 85 246 00 39. We are grateful to Dr. s. Klotz for helpful discussions and an anonymous referee for his usehl comments. References
[I] Mao, H. K., Bell, P. M., Shaner, J. W. and Steinberg, D. J. (1978). Specific volume measurements of Cu, Mo, Pd, and Ag calibration of the R, fluorescence pressure gauge from 0.06 to I Mbar. J. Appl. Pliys., 49, 3276. [2] Mao, H. K., Xu, J. A. and Bell, P. M., J. (1986). Calibration of the ruby gauge to 800kbar under quasi-hydrostatic conditions. Geophys. Res. E, 91, 4673. [3] McCumber, D. E. and Sturge, M. D. (1963). Linewidth and temperature shift of the R lines in ruby. 1 Appl. fhys., 34(6), 1682.

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[4] Bamett, J. D., Block, S. and Piermarini, G. J. (1973), An optical fluorescence system for quantitative pressure measurement in the diamond anvil cell. Rev. Sci. Instrzmi., 44, 1. [5] Noak, R. A. and Holzapfel, W. B. (1978). Calibration of the ruby pressure scale at low temperatures. Proc. 6th AIRAPT Conference, Plenum Press, New York, p. 748. [6] Nakamura, Y., Fijishiro, 1. and Taniguchi, K. (1991). Hysteresis of ruby fluorescent line by pressure and annealing effect. H i g h Presswe Research, 6 , 301. [7] Powell, R. C., DiBartolo, B., Birang, B. and Naiman, C. S. ( I 966). Temperature dependence of the widths and positions of the R and N lines in heavily doped ruby. 1 Appl. Phys., 37,4973. [8] Maiman, T. H., Hoskins, R. H., D'Haenens, 1. J., Asawa, C. K. and Evtuhov, V (1961). Stimulated optical emission in fluorescent solids. 11. Spectroscopy and stimulated emission in ruby. Phys. Rev., 123, 1151. [9] Mc Clure, D. S. (1 962). Optical spectra of transition metal-ions in corundum, 1 Chein. Phys., 36. 2757. [lo] Sugano, S. and Tanabe, Y. (1958). Absorption spectra ofCr3+ in A1203. 1 Phys. SOC. Japan, 13, 880. [I 11 Mac Farlane, R. M., (1965). On the ground state splitting of ruby. 1 Chetn. Phys., 41,442. [I21 Nelson, D. F. and Sturge, M. D. (1965). Relation between absorption and emission in the region of the R lines of Ruby. Pbys. Rev. A, 137, 11 17. [13] Curie, D. (1 968). Champ Cristallin et Lutnitiescence, Gauthier-Villars, Paris. [I41 Canny, B., Chervin, J. C., Curie, D., Venkatapen, V and Jing Qing, L. (1988). Raman effect and phonon replicas in Ruby and Alexandrite crystals. In: Boulon, G., Jorgensen, C. K. and Reisfeld, R. (Eds.), French-Israeli Workshop oti Solid State Lasers, Vol. 74, 12-14 December. [15] Williams, Q. and Jeanloz, R. (1985). Pressure shift of Cr3+-ion-pair emission lines in ruby. Phys. Rev. B, 31,1449. [16] Le Rubis SA, R. S. A. RN 85- BP 16,38560 Janie, France. [I71 Chervin, J. C., Canny, B., Besson, J. M. and Pruzan, Ph. (1995). A diamond anvil cell for infrared microspectroscopy. Rev. Sci. Aistrzmt.,66, 2595. (181 Weinstein, B. A. (1986). Ruby thermometer for cryobaric diamond-anvil cell. Rev. Sci. Instriuii., 57, 9 10. [19] Chervin, J. C., Canny, B., Gauthier, M. and Pruzan, Ph. (1993). Micro-Raman at low temperature and very high pressure. Rev. Sci.I~isb-trin., 64, 203. [20] Leger, J. M., Chateau, C. and Lacam, A. (1990). SrB,07: Sm2+ pressure optical sensor: Investigations in the megabar range. 1 Appl. Phys., 68,2351. [2 I ] Datchi, F., Le Toullec, R. and P. Loubeyre. ( I 997). Improved calibration of the SrB307: SmZf optical pressure gauge: Advantages at very high pressures and high temperatures. 1 Appl. P/i.vs., 81, 3333. [22] Yamaoka, S., Shimomura, 0. and Fukunaga, 0. (1980). Simultaneous measurements of temperature and pressure by the ruby fluorescence line. Proc. Japan Acad., 56B(3), 103.