Eur. Phys. J. Special Topics 169, 237242 (2009) c EDP Sciences, Springer-Verlag 2009 DOI: 10.

1140/epjst/e2009-00998-3

THE EUROPEAN PHYSICAL JOURNAL

SPECIAL TOPICS

Review

The microcalorimeter X-ray detector: A true paradigm shift in X-ray spectroscopy

T. Jach1,a , J.N. Ullom2 , and W.T. Elam3
1 2 3

National Institute of Standards and Technology, Gaithersburg, MD 20899, USA National Institute of Standards and Technology, Boulder, CO 80305, USA Applied Physics Laboratory, University of Washington, Seattle, WA 98105, USA

Abstract. The microcalorimeter x-ray detector registers the heat deposited in an absorber from individual x-ray photons by means of a sensitive thermometer. It combines advantages of wavelength-dispersive and energy-dispersive detectors: relatively high energy resolution over a broad energy spectrum. Operating at very low temperatures reduces the noise, making the high energy resolution possible. The absorber can be tailored to any energy range, from soft x-rays to gamma rays. After many years of development, several designs have reached a level of performance and reliability that makes them competitive x-ray detectors for many kinds of experiment. We survey current microcalorimeter detectors using several dierent thermometers. Their applications already run from chemical analysis to plasma physics and x-ray astronomy. We describe two examples of how the microcalorimeter detector can enable novel determinations in x-ray physics.

1 Introduction
The microcalorimeter detector diers from other x-ray detectors in that it registers the energy deposited by individual photons as heat. The detector consists of an absorber and a sensitive thermometer. The heat pulse is directly proportional to the energy deposited, and the duration of the pulse depends on the thermal conductivity to an outside reservoir. The limiting resolution of the detector is determined by thermal power uctuations in the conductivity to the reservoir [1]. With a low heat capacity absorber and an operating temperature below 100 mK the uctuations are reduced to the order of 1 eV. The microcalorimeter is thus a detector whose resolution approaches wavelength-dispersive detectors, while its spectral range, determined by the absorber and the thermometer, is comparable to energy-dispersive (SiLi or SDD) detectors. The active area of an individual detector is necessarily low, to maintain a small heat capacity. Several variants of microcalorimeter detector have proven successful. Examples of low heat capacity absorbers are Bi, Sn, and Ta. Three dierent schemes have been used for the thermometer. A doped semiconductor has been used as a low-temperature thermistor [2]. A second type of thermometer, the transition edge sensor (TES), uses the resistive change of a thin metal lm biased at the transition temperature between superconducting and normal [3]. Finally, the change in paramagnetic susceptibility with temperature can be measured using a superconducting quantum interference device (SQUID) sensor [4]. The detectors have already been employed in a broad variety of x-ray applications. In conjunction with an electron microscope, quantitative analyses of stoichiometric and nonstoichiometric compounds have been demonstrated using detectors with TES thermometers [57]. Detectors using semiconductor thermistors have successfully obtained spectra of x-rays
a

e-mail: terrence.jach@nist.gov

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produced by highly ionized atoms in electron-beam ion traps (EBIT) [8,9]. A detector using a TES thermometer has been used to perform x-ray uorescence analyses of archaeological samples excited by synchrotron radiation [10]. Finally, detectors using semiconductor thermistors have already demonstrated the ability to observe cosmic x-rays in space [11]. This last is expected to be one of the major applications of microcalorimeter detectors using all types of thermometer.

2 New types of application

The microcalorimeter detector is not merely an alternative to the existing x-ray detectors; it is an enabling technology by which we can envision novel x-ray experiments. The purpose of this paper is to describe new applications where the use of microcalorimeter detectors will allow us to carry out measurements that were previously not practical or not even possible. We describe two experiments that open up new approaches to measurement in spectroscopy and chemical analysis. The rst experiment is a demonstration of the broad energy resolution capability of the microcalorimenter detector for x-ray line calibrations. The most recently published review of x-ray transition energies [12] tabulates the best values for principle and satellite lines which can be obtained from an analysis of existing measurements and calculations. These values are arrived at by a complex process of interpreting, correcting, and extrapolating transition energies from existing values in the published literature. The experimental uncertainties of some lines at intermediate energies (<10 keV) exceed 5 eV. The uncertainties of many calculated lines are even greater. In no case is it possible to contemplate an accurate comparison in the same spectrum between lines of widely diering energies such as K and L series lines of the same elements or between K lines of elements with a large dierence in Z. We shall demonstrate the extent to which the high resolution of the TES microcalorimeter, combined with its good linearity, allows us to perform this type of measurement. A second type of experiment involves instances where core holes are lled by valence band electrons. These cases typically involve soft x-ray transitions, and the x-ray uorescence spectrum is determined by the density of states of the valence band of the chemical compound being studied. While x-ray emission spectra (XES) of localized energy regions are routinely obtained using a grating spectrometer and an intense excitation source (such as synchrotron radiation), it is often desirable to obtain spectra from multiple elements simultaneously. With electron excitation (e.g. in microanalysis) several wavelength-dispersive detectors using multilayers or crystals of large d-spacing may be used simultaneously to acquire data on several lines. They do not provide the resolution equivalent of a grating spectrometer. We shall demonstrate that the microcalorimeter detector is already capable of observing valence band x-rays at a resolution equivalent to soft x-ray wavelength-dispersive detectors. The possibility exists of a microcalorimeter detector approaching the resolution of a grating spectrometer with a range that would cover many elements.

3 Experimental details
Our microcalorimeter detector consists of a 400 m square Bi absorber and a TES consisting of a Mo superconducting lm reduced in Tc to approximately 100 mK by the proximity eect of a Cu overlayer. The absorber was tailored to an energy range of 8 keV. The detector was operated in equilibrium with a 70 mK thermal reservoir, produced by an adiabatic demagnetization refrigerator (ADR). The temperature dierence is due to the thermal feedback employed to lock the TES to a specic temperature on the superconducting-normal metal curve [13]. A single ADR cycle was capable of keeping our detector cold for approximately 12 h. For experimental reasons, we typically take spectra over a 6 h period. The detector was stable to better than 1 eV/h during that time [14]. Because of the small resistive change of the voltage-biased thin lm at the superconductingnormal transition, the temperature pulses converted into current pulses are initially amplied

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Fig. 1. Microcalorimeter spectrum of NIST K411 glass excited by electrons at 12 keV.

by Josephson junction electronics using a single SQUID followed by a 100 SQUID array. The Josephson voltage produced at the multiple SQUID stage can then be amplied by conventional room-temperature electronics. An output signal then fed back to the initial SQUID stage maintains a very linear response, and the feedback signal is actually the pulse which is measured. The energy resolution of the spectrum depended on the method of signal analysis. For the rst experiment of comparing x-ray line calibration energies, we used analog signal processing and pulse height analysis. When adjusted to the longer decay time of microcalorimeter pulses ( 200 s) this gave us FWHM linewidths of 8 eV11 eV. For the optimal resolution, which was used in the spectroscopy of the valence band of BN, we digitized pulses as they came in and stored the data. The pulses were afterwards processed by constructing an optimal digital lter which gave a resolution (after deducting the natural linewidths) of 4.4 eV 0.2 eV for the Mn K1,2 lines from Fe55 . The experiments were carried out using electron beam excitation in an electron microscope. We used small samples consisting of a NIST Standard Reference Material Glass K411 [15] and a single crystal of hexagonal BN. The samples were excited using an electron beam of 12 keV kinetic energy with a current of approximately 10 nA. The count rates were in the range of 40 c/s200 c/s. High-resolution XES of the N KV transition was also performed for comparison on a hexagonal BN sample on Beamline 8.0.1 of the Advanced Light Source using a Rowland circle grating spectrometer and a channel plate detector. In that case, the N K line was excited by a monochromatized undulator beam.

4 Application I: Comparison of X-ray line energies

The TES microcalorimeter detector does not have an absolute energy scale. It is necessary to recalibrate the scale by means of standard x-ray emission lines after each ADR cooling cycle. A combination of carefully chosen detector response characteristics and the feedback to the initial SQUID stage results in a calibration scale between pulse height and photon energy that is very linear, requiring only a quadratic correction term of the order of 2 103 . Fig. 1 shows a microcalorimeter spectrum of the K411 reference glass, containing Si, Mg, Ca, and Fe after calibration. Before calibration, the spectrum occurs on a nominal energy scale. The energies of the Fe K, Ca K, Si K, and Fe L lines were all tted by gaussian peaks. The tting did not take into account line splittings beyond the K1,2 or K1,3 . Satellite lines were not included in the ts.

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Fig. 2. Fits to selected x-ray uorescence lines of K411 glass using the nominal energy scale.

A series of ts to these lines is shown in Fig. 2. The nominal line energies obtained from the tted peak positions were then plotted against the energies obtained from experimental values in ref. [12] to obtain a quadratic calibration curve. The deviations of tted values from the experimental table energies are plotted against the resulting calibrated energies in Fig. 3. The deviations were relatively small, with a standard error of 0.67 eV. This is noteworthy for two reasons. First, it indicates that the quadratic t to the energy scale of the microcalorimeter was already quite good, and that the nonlinear correction to the energy scale was small. Second, we are really testing for the rst time a coherent energy scale for ref. [12] in a way that has not been carried out previously. A comparison between the energies of the Fe K1 and the Fe L lines could, in principle, be made in the same spectrum with a SiLi detector, but not with the resolution that the TES microcalorimeter is capable of here. Similarly, a comparison between the energy of the Fe K1 [16] and the Ca K [17] measured values is a comparison between two experimental values that were determined under dierent circumstances. This should only be regarded as a preliminary demonstration of the accuracy that is possible. A proper measurement with greater count statistics would take account of asymmetric eects in lineshape due to multiplet and satellite transitions [16,18].

5 Application II: Valence band X-ray emission spectra

With few exceptions, K lines of x-ray emission spectra show very little deviation as a result of chemical bonding [19]. The exceptions are atoms where a 1s core hole is lled with an electron from the valence band. In low-Z elements, such as nitrogen, the width of the valence band represented by the hybridization of the bonding levels can represent almost 10% of the transition energy. Soft x-ray emission spectra are an important tool to determine the density of states of chemical compounds. While high resolution can be achieved for soft x-rays by means of grating spectrometers, it would be desirable to obtain the spectra of all the elements at the same time.

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Fig. 3. Deviations of tted line energies measured in the NIST K411 glass from the experimental energies of ref. [12].

Fig. 4. Spectra of the N KV emission from hexagonal BN: (a) spectrum obtained with a high resolution grating spectrometer excited by synchrotron radiation at the ALS (dotted); (b) spectrum obtained by the TES with electron excitation (histogram); (c) spectrum (a) broadened with a 4 eV instrument function (solid line). Details in the text.

Figure 4 shows a spectrum of soft x-ray emission at the N K energy from a sample of hexagonal BN. The crystal was excited by a monochromatic beam of x-rays at 422 eV on Beamline 8.0.1 at the Advanced Light Source (dots). The spectrum was accumulated on a spherical grating spectrometer with a resolution of 0.5 eV. The emission spectrum shows features associated with the molecular orbitals that participate in the bonding of hexagonal BN [20]. The histogram in Fig. 4 is a spectrum of hexagonal BN using the microcalorimeter detector with excitation by an electron probe at a beam energy of 12 keV. The solid line in the gure was obtained by convolving the high resolution grating spectrum from the ALS with a 4 eV gaussian instrument function. When the ALS spectrum is broadened to a resolution comparable to that of the microcalorimeter, the BN spectrum from the electron beam and the x-ray excited spectrum, to within statistical errors, are in good agreement. At our current resolution, the

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microcalorimeter spectrum already displays the broad outline of the BN valence band. We anticipate that with a suitable selection of design characteristics, a detector with a limited range of 1 keV could have a resolution of 0.8 eV. This would allow us to see the chemical bonding eects in core-valence transitions from a variety of low-Z compounds.

6 Conclusions
While microcalorimeter x-ray detectors are still at a developmental stage, some aspects of their novelty should be apparent. These detectors are not just a variation on traditional x-ray detectors. With a combination of broad energy range, high linearity, and good energy resolution, they oer new possibilities in x-ray metrology that were previously not available. Routine operations at temperatures of 100 mK have become reliable due to improvements in closed cycle and adiabatic demagnetization refrigeration. We can look forward to a comparison of x-ray line energies with increasing accuracy. Studies of x-ray satellites, relative line intensities, and chemical shifts of emission lines should be easier to carry out on a much broader scale.
We acknowledge the assistance of J. Denlinger and other sta of the Advanced Light Source. The Advanced Light Source is supported by the Director, Oce of Science, Oce of Basic Energy Sciences, of the U.S. Department of Energy under Contract No. DE-AC02-05CH11231.

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