Nuclear magnetic resonance (NMR) technologies, such as NMR spectrometers and imaging systems, allow researchers to observe certain magnetic properties of atomic nuclei. These observations can be used to study basic chemical and physical properties of molecules or other small objects. NMR technologies are commonly used, for instance, to perform research on organic and inorganic molecules in the fields of medicine, chemistry, biology, and pharmacology.
NMR measurements are typically performed by an NMR probe that receives a sample to be studied. The sample is placed in a static magnetic field which aligns the magnetic dipoles of its atomic nuclei. Thereafter, the NMR probe applies a time-varying radio-frequency (RF) magnetic field to the sample to perturb the alignment of the magnetic dipoles. Next, the NMR probe detects the magnetic field generated by the perturbed nuclei as they return to their aligned positions. Finally, the detected magnetic field is analyzed to identify various aspects of the sample, such as its composition, the structure of its molecules, and other valuable information.
The NMR probe typically comprises a probe coil that generates the time-varying magnetic field to be applied to the sample and/or detects the magnetic field generated by the perturbed atomic nuclei as they return to their aligned positions. These magnetic fields typically oscillate in the radio-frequency (RF) range. Accordingly, the probe coil may be referred to as an RF transmitter coil, an RF receiver coil, or an RF transmitter/receiver coil. The probe coil is generally tuned to generate the time-varying magnetic field at the resonance frequency of the atomic nuclei, and to detect magnetic oscillations at the resonance frequency of the atomic nuclei.
The performance of the probe coil can be evaluated according to its quality factor (Q-factor), which indicates its bandwidth relative to a resonant frequency of interest. Q is inversely proportional to the resistance of the coil. Thus, a high-Q coil has lower thermal noise and so, if tuned to the frequency of the sample's nuclei, can detect their magnetic oscillations with high sensitivity. Accordingly, other things being equal, a probe coil with a higher Q-factor can produce higher-sensitivity measurements than a probe coil with a lower Q-factor.
One way to improve the Q-factor of an NMR probe coil is by forming it with a superconducting material. The superconducting material can enhance the sensitivity of the coil, allowing it to respond to relatively small magnetic fields of the sample. To achieve superconductivity, however, the superconducting material must be maintained in a cryogenically cooled environment, such as a cryogenically cooled vacuum chamber.
The vacuum chamber prevents the NMR probe coil and other cryogenic structures from absorbing heat through conduction. Nevertheless, it still allows the NMR probe coil and other structures to absorb heat through radiation, such as black-body radiation from the sample being measured. Unfortunately, this absorption of black-body radiation can lead to thermal gradients in the sample, which tends to deteriorate measurements obtained by the NMR probe. In addition, it adds to the heat load that must be removed by the cryogenic cooling system in order to maintain a steady and low temperature.
In a representative embodiment, an NMR probe comprises a substrate, a probe coil formed over the substrate and comprising a superconducting material, and a plurality of patches formed over the substrate and around the probe coil, wherein each of the patches is configured to reflect infrared radiation (IR) from a sample tube within the NMR probe.
In another representative embodiment, an NMR device comprises a center tube configured to receive an sample tube within an annular space, a gas source configured to supply a stream of gas to a portion of the annular space between a watt of the center tube and a wall of the sample tube, a cooled vacuum chamber surrounding the center tube, and a probe structure disposed within the vacuum chamber and comprising a substrate, a superconducting NMR probe coil formed over the substrate, and a plurality of patches formed over the substrate around the NMR probe coil, wherein each of the patches is configured to reflect IR radiation transmitted from the center tube to the vacuum chamber.
In still another representative embodiment, a method of forming an NMR probe comprises forming a first layer of superconducting material over a substrate, forming a second layer of normal metal over the layer of superconducting material, etching the first and second layers to form a spiral or interdigital shaped NMR probe coil of the superconducting material and the normal metal, and etching the first and second layers to form a plurality of patches around the NMR probe coil, wherein the patches are configured to reflect IR radiation from a sample tube within the NMR probe.
The described embodiments are best understood from the following detailed description when read with the accompanying drawing figures. It is emphasized that the various features are not necessarily drawn to scale. In fact, the dimensions may be arbitrarily increased or decreased for clarity of discussion. Wherever applicable and practical, like reference numerals refer to like elements.
In the following detailed description, for purposes of explanation and not limitation, representative embodiments disclosing specific details are set forth in order to provide a thorough understanding of the present teachings. However, it will be apparent to one having ordinary skill in the art having had the benefit of the present disclosure that other embodiments according to the present teachings that depart from the specific details disclosed herein remain within the scope of the appended claims. Moreover, descriptions of well-known apparatuses and methods may be omitted so as to not obscure the description of the example embodiments. Such methods and apparatuses are clearly within the scope of the present teachings.
The terminology used herein is for purposes of describing particular embodiments only, and is not intended to be limiting. The defined terms are in addition to the technical and scientific meanings of the defined terms as commonly understood and accepted in the technical field of the present teachings.
As used in the specification and appended claims, the terms ‘a’, ‘an’ and ‘the’ include both singular and plural referents, unless the context clearly dictates otherwise. Thus, for example, ‘a device’ includes one device and plural devices.
As used in the specification and appended claims, and in addition to their ordinary meanings, the terms ‘substantial’ or ‘substantially’ mean to within acceptable limits or degree.
As used in the specification and the appended claims and in addition to its ordinary meaning, the term ‘approximately’ means to within an acceptable limit or amount to one having ordinary skill in the art, For example, ‘approximately the same’ means that one of ordinary skill in the art would consider the items being compared to be the same.
The representative embodiments relate generally to NMR measurement technologies such as NMR spectrometers and imaging systems. Certain embodiments provide an NMR probe comprising a superconducting NMR probe coil and a plurality of IR reflection patches formed on a substrate. The IR reflection patches reflect infrared radiation such as black-body radiation to prevent it from being absorbed by the substrate. This can reduce or eliminate thermal gradients in a sample being measured by the NMR probe without substantially degrading an RF quality factor of the NMR probe coil or blocking an RF magnetic field generated by the coil.
Referring to
Sample tube 105 and center tube 110 are separated by an annular space, and a gas stream (e.g., nitrogen or dry air) is passed through the annular space to control the temperature of sample tube 105. The temperature is typically controlled so that it remains substantially uniform from one end of sample tube 105 to the other. Moreover, the temperature of sample tube 105 and center tube 110 is typically maintained close to room temperature, and it can be controlled to a high level of accuracy, e.g., to within about a tenth of a degree Centigrade.
The temperature of sample tube 105 and center tube 110 is generally controlled through the use of a feedback control system. This system pumps the gas stream from one end of the probe, through the annular space, and out the other end of the probe. Before entering the annular space, the gas stream passes by a heater that heats it to the desired temperature. The gas stream then passes by a sensor that determines the temperature of the gas. The detected temperature is fed back to the control system so that it can adjust the heater to achieve the desired temperature.
Vacuum chamber 115 is hermetically sealed to create a vacuum between NMR probe coil 120 and the outside environment, In an embodiment, the vacuum chamber is cryogenically cooled. The vacuum prevents heat conduction, or convection, from affecting the temperature of NMR probe coil 120 or the outside environment. Within this vacuum, NMR probe coil 120 is cryogenically cooled to a temperature of about 20K or less in order to achieve superconductivity. This cooling can be accomplished, for instance, by connecting a heat exchanger to a substrate of NMR probe coil 120.
Although the vacuum prevents heat conduction between NMR probe coil 120 and the outside environment, thermal energy can nevertheless be transferred in the form of radiation, such as infrared radiation. For example, black-body radiation from sample tube 105 or center tube 110 may emanate toward vacuum chamber 115 and then be absorbed by NMR probe coil 120. In general, black-body radiation from a room temperature object peaks at a wavelength of about 10 μm, which is within a range where a typical sapphire substrate of NMR probe coil 120 is strongly absorbing.
The absorption of black-body radiation by NMR probe coil 120 and other cryogenic structures can cause a gradual decrease in the temperature of the gas stream along its length. In other words, the gas stream may cool down between the time it enters and leaves the annular space between sample tube 105 and center tube 110. This cooling can affect the temperature of the sample located in sample tube 105, potentially producing temperature gradients and/or convection currents in the sample. These temperature gradients and/or convection currents can prevent NMR probe 100 from producing NMR measurements with good lineshape, and they may require more complicated shimming of NMR probe 100. The absorption of black-body radiation by NMR probe coil 120 and other cryogenic structures also adds to the heat load that must be removed from vacuum chamber 115. In a typical implementation, this load can require 5 to 7 kW of alternating current (AC) line power to maintain NMR probe coil 120 at a steady and low temperature.
In view of these and other effects of heat transfer within NMR probe 100, it can be beneficial to prevent NMR probe coil 120 from absorbing black-body radiation, One way of doing this, as will be described below, is to form IR, reflection patches on NMR probe coil 120. These IR reflection patches can reflect black-body radiation to prevent heat transfer without interfering with the transmission of RF fields between NMR probe coil 120 and the sample. This can reduce or eliminate thermal gradients in the sample, and it can potentially reduce the radiated load by a factor of three or more, enabling the use of more economical cooling systems.
Referring to
The configuration of probe coil 205 is one of various alternative coil configurations that can be used in an NMR probe. For high frequencies, such as 400 to 900 MHz for measuring 1H and 19F, the configuration with interdigital capacitors (or interwoven combs), as shown in
Probe coil 205 is formed of a thin film of material with a normal-metal overlayer. The HTS material and the normal metal are deposited on substrate 210 and then patterned in the shape of a rectangle with curved corners. In a typical configuration, the elements of probe coil 205 are separated from each other by about 30 to 100 μm. The HTS material forms a tuned circuit used to perform transmission and/or reception of electromagnetic signals with respect to the sample. The normal-metal layer prevents burn-out of the HTS film under high-power circumstances by what is called an “RF quench.” It can also prevent degradation by environmental contaminants.
The HTS material can comprise, for instance, yttrium barium copper oxide (YBCO) or various other rare-earth barium copper oxides (ReBCO). Substrate 210 typically comprises a material such as synthetic sapphire. The HTS material is typically formed through an epitaxial growth process in which it is deposited on the substrate by sputtering, evaporation, or one of various other deposition techniques. In some examples, substrate 210 is about 400 micrometers (μm or microns) thick and the HTS material is about 0.3 micrometers thick. The normal-metal can comprise, for instance, gold, silver, or another relatively non-reactive and electrically conductive layer, or a combination of metals such as a thin layer of titanium with a thicker layer of gold on top of it.
NMR probe coil structure 200 is typically used in a cryogenic probe in conjunction with a heat exchanger or other temperature control mechanism. For example, in some embodiments, two probe coils 205 are placed on opposite sides of a sample tube, and a substrate supporting each coil is attached to a heat exchanger. The heat exchanger provides cooling and temperature control of each probe coil 205. During operation, the probe coils 205 are typically cooled to a temperature of about 20 K or lower, which tends to minimize electrical noise (“Johnson” or “thermal” noise) in the HTS material, and can substantially increase its amplitude and power sensitivity.
The windings of probe coil 205 can be inductively coupled to a coupling loop that is electrically connected to an NMR spectrometer. The coupling loop can provide RF energy to probe coil 205 to excite NMR resonance and it can receive a response induced in probe coil 205 from the sample and transmit the response to the spectrometer for processing, recording, and display.
In some embodiments, probe coil 205 is a spiral arranged in a back-to-back configuration with another probe coil wound in the opposite direction. In other words, probe coil 205 can be one of two counterwound spirals. Various examples of counterwound spirals are described in commonly owned U.S. Pat. No. 7,701,217, by Withers et al., the disclosure of which is hereby incorporated by reference. In one example embodiment, the counterwound spirals are configured to resonate at around 150 MHz to detect 13C in a 14.1-T magnet. A probe with these spirals can be designed to accept samples in 1.5-mm outer-diameter tubes, for example.
As indicated by the foregoing, an exposed portion of probe coil 205 is formed by a normal-metal such as gold, which is highly reflective of IR radiation. However, as illustrated in
Referring to
As illustrated by the close-up of
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As illustrated in
Probe coil 205 and IR reflection patches 405 are typically formed of the same material and by similar processes, For example, they can both be formed by depositing a layer of YBCO and then a layer of gold on substrate 210, and then etching both of the layers using an etching process such as ion milling, Because the formation of probe coil 205 alone typically requires all of these steps, IR reflection patches 405 can be formed with minimal additional cost compared with the probe coil 205 by itself.
In the example of
Referring to
In general, gold is very reflective in the infrared range, so forming the patches of gold can reduce the thermal absorption of NMR probe coil structure 400 due to IR radiation. However, gold can also block RF energy, so it may interfere with the transmission and reception of signals by probe coil 205. Accordingly, the exposed portions of substrate 210 are formed between IR reflection patches 405 in order to allow RF penetration. As indicated above, these separations can be formed by an etching process such as ion milling, which is used to form probe coil 205.
The dimensions and geometry of IR reflection patches 405 can affect the performance of probe coil 205 in various ways. For example, if the patches are too large, persistent currents may arise in the superconductor material. These persistent currents create their own magnetic field, which can disturb the homogeneity of the static magnetic field and interfere with NMR measurements. On the other hand, if the patches are too small, the proportional area covered by the patches, or filling factor, may decrease. A reduction in filling factor tends to increase the amount of IR energy absorbed by substrate 210, which can contribute to thermal gradients in an NMR sample.
Persistent currents can generally be maintained within an acceptable range by forming IR reflection patches 405 such that their largest dimension, or superconducting structure, has a maximum line width less than or equal to about 12 μm or 10 μm. As an example,
Although not shown in the drawings, IR reflection patches 405 can also be combined with other approaches for reducing heat transfer between a sample and NMR probe coil structure 400. For example, one additional approach is to wrap the outside of center tube 110, in the vacuum space, with glass fibers capable of scattering or reflecting infrared radiation. In addition, IR reflection patches 405 can also be modified to have various alternative geometries not shown in the drawings. For example, they can be formed as rectangles, elongated strips, various other polygonal shapes, irregular shapes, and so on.
Referring to
After the HTS material is grown on the substrate, a layer of normal-metal is formed on the substrate over the HTS material (S610). Among other things, this layer can protect he HTS against so-called “RF quench” and environmental contamination or degradation, and it can be used to form IR reflection patches such as those illustrated in
Next, the layers of normal-metal and HTS material are etched to form a tuned circuit in the form of a spiral such as that illustrated in
In experimental examples of NMR probe coil structure 400, it has been determined that the presence of reflection patches 405 does not significantly reduce the Q-factor or sensitivity of probe coils 205. It has also been determined that the IR reflection patches 405 do not substantially block RF magnetic fields generated by probe coils 205, which also avoids a reduction in the sensitivity of probe coils 205.
For example, in some experiments, it has been determined that the Q-factor of probe coil 205 with IR reflection patches 405 is similar to that of probe coil 205 without IR reflection patches 405. It has also been observed that the resonant frequencies of probe coil 205 appear to be unaffected by reflection patches 405. If the RF magnetic fields of probe coils 205 are blocked by the patches, the coil inductance is reduced and its frequency rises.
Where an RF magnetic field such as that generated by probe coil 205 of
While example embodiments are disclosed herein, one of ordinary skill in the art appreciates that many variations that are in accordance with the present teachings are possible and remain within the scope of the appended claims. For example, although various embodiments are described in relation to planar coils, these embodiments could be modified to include cylindrical coils. The invention therefore is not to be restricted except within the scope of the appended claims.