A diamond anvil cell (DAC) is a high-pressure device used in geology, engineering, and materials science experiments. It permits the compression of a small (sub-millimeter-sized) piece of material to extreme pressures, typically up to around 100–200 gigapascals, although it is possible to achieve pressures up to 770 gigapascals (7,700,000 bars or 7.7 million atmospheres).
The device has been used to recreate the pressure existing deep inside planets to synthesize materials and phases not observed under typical ambient conditions. Notable examples include the non-molecular ice X, polymeric nitrogen and metallic phases of xenon, lonsdaleite, and potentially metallic hydrogen.
A DAC consists of two opposing diamonds with a sample compressed between the polished culets (tips). Pressure may be monitored using a reference material whose behavior under pressure is known. Common pressure standards include ruby fluorescence, and various structurally simple metals, such as copper or platinum. The uniaxial pressure supplied by the DAC may be transformed into uniform hydrostatic pressure using a pressure-transmitting medium, such as argon, xenon, hydrogen, helium, paraffin oil or a mixture of methanol and ethanol. The pressure-transmitting medium is enclosed by a gasket and the two diamond anvils. The sample can be viewed through the diamonds and illuminated by X-rays and visible light. In this way, X-ray diffraction and fluorescence; optical absorption and photoluminescence; Mössbauer, Raman and Brillouin scattering; positron annihilation and other signals can be measured from materials under high pressure. Magnetic and microwave fields can be applied externally to the cell allowing nuclear magnetic resonance, electron paramagnetic resonance and other magnetic measurements. Attaching electrodes to the sample allows electrical and magnetoelectrical measurements as well as heating up the sample to a few thousand degrees. Much higher temperatures (up to 7000 K) can be achieved with laser-induced heating, and cooling down to millikelvins has been demonstrated.
Principle The operation of the diamond anvil cell relies on a simple principle:
where is the pressure, the applied force, and the area. Typical culet sizes for diamond anvils are 100–250 micrometres (μm), such that a very high pressure is achieved by applying a moderate force on a sample with a small area, rather than applying a large force on a large area. Diamond is a very hard and virtually incompressible material, thus minimising the deformation and failure of the anvils that apply the force.
History
The study of materials at extreme conditions, high pressure and high temperature uses a wide array of techniques to achieve these conditions and probe the behavior of material while in the extreme environment. Percy Williams Bridgman, the great pioneer of high-pressure research during the first half of the 20th century, revolutionized the field of high pressures with his development of an opposed anvil device with small flat areas that were pressed one against the other with a lever-arm. The anvils were made of tungsten carbide (WC). This device could achieve pressure of a few gigapascals, and was used in electrical resistance and compressibility measurements.
The first diamond anvil cell was created in 1957–1958. The principles of the DAC are similar to the Bridgman anvils, but in order to achieve the highest possible pressures without breaking the anvils, they were made of the hardest known material: a single crystal diamond. The first prototypes were limited in their pressure range and there was not a reliable way to calibrate the pressure.
The diamond anvil cell became the most versatile pressure generating device that has a single characteristic that sets it apart from the other pressure devices – its optical transparency. This provided the early high pressure pioneers with the ability to directly observe the properties of a material while under pressure in two ways: With just the use of an optical microscope, phase boundaries, color changes and recrystallization could be seen immediately, while x-ray diffraction or spectroscopy required time to expose and develop photographic film. The potential for the diamond anvil cell was realized by Alvin Van Valkenburg while he was preparing a sample for IR spectroscopy and was checking the alignment of the diamond faces.
The diamond cell was created at the National Bureau of Standards (NBS) by Charles E. Weir, Ellis R. Lippincott, and Elmer N. Bunting. Within the group, each member focused on different applications of the diamond cell. Van Valkenburg focused on making visual observations, Weir on XRD, Lippincott on IR Spectroscopy. The group members were well experienced in each of their techniques before they began outside collaboration with university researchers such as William A. Bassett and Taro Takahashi at the University of Rochester.
During the first experiments using diamond anvils, the sample was placed on the flat tip of the diamond (the culet) and pressed between the diamond faces. As the diamond faces were pushed closer together, the sample would be pressed and extrude out from the center. Using a microscope to view the sample, it could be seen that a smooth pressure gradient existed across the sample with the outermost portions of the sample acting as a kind of gasket. The sample was not evenly distributed across the diamond culet but localized in the center due to the "cupping" of the diamond at higher pressures. This cupping phenomenon is the elastic stretching of the edges of the diamond culet, commonly referred to as the "shoulder height". Many diamonds were broken during the first stages of producing a new cell or any time an experiment is pushed to higher pressure. The NBS group was in a unique position where almost endless supplies of diamonds were available to them. Customs officials occasionally confiscated diamonds from people attempting to smuggle them into the country. Disposing of such valuable confiscated materials could be problematic given rules and regulations. One solution was simply to make such materials available to people at other government agencies if they could make a convincing case for their use. This became an unrivaled resource as other teams at the University of Chicago, Harvard University, and General Electric entered the high pressure field.
During the following decades DACs have been successively refined, the most important innovations being the use of gaskets and the ruby pressure calibration. The DAC evolved to be the most powerful lab device for generating static high pressure. The range of static pressure attainable today extends to 640 GPa, much higher than the estimated pressures at the Earth's center (~360 GPa).
Components There are many different DAC designs but all have four main components:
Force-generating device Relies on the operation of either a lever arm, tightening screws, or pneumatic or hydraulic pressure applied to a membrane. In all cases the force is uniaxial and is applied to the tables (bases) of the two anvils.
Two opposing diamond anvils Made of high gem quality, flawless diamonds, usually with 16 facets, they typically weigh to carat (25 to 70 mg). The culet (tip) is ground and polished to a hexadecagonal surface parallel to the table. The culets of the two diamonds face one another, and must be perfectly parallel in order to produce uniform pressure and to prevent dangerous strains. Specially selected anvils are required for specific measurements – for example, low diamond absorption and luminescence is required in corresponding experiments.
Gasket A gasket used in a diamond anvil cell experiment is a thin metal foil, typically 0.3 mm in thickness, which is placed in between the diamonds. Desirable materials for gaskets are strong, stiff metals such as rhenium or tungsten. Steel is frequently used as a cheaper alternative for low pressure experiments. The above-mentioned materials cannot be used in radial geometries where the x-ray beam must pass through the gasket. Since they are not transparent to X-rays, if X-ray illumination through the gasket is required, lighter materials such as beryllium, boron nitride, boron or diamond are used as a gasket. Gaskets are preindented by the diamonds and a hole is drilled in the center of the indentation to create the sample chamber.
Pressure-transmitting medium The pressure transmitting medium is the compressible fluid that fills the sample chamber and transmits the applied force to the sample. Hydrostatic pressure is preferred for high-pressure experiments because variation in strain throughout the sample can lead to distorted observations of different behaviors. In some experiments stress and strain relationships are investigated and the effects of non-hydrostatic forces are desired. A good pressure medium will remain a soft, compressible fluid to high pressure. +Pressure-transmitting medium Gases Liquids Solids Helium (He) Neon (Ne) Argon (Ar) Nitrogen (N) 4:1 Methanol:Ethanol Silicone oil Fluorinert Daphne 7474 Cyclohexane Sodium chloride (NaCl)
The full range of techniques that are available has been summarized in a tree diagram by William Bassett. The ability to utilize any and all of these techniques hinges on being able to look through the diamonds which was first demonstrated by visual observations.
Measuring pressure The two main pressure scales used in static high-pressure experiments are X-ray diffraction of a material with a known equation of state and measuring the shift in ruby fluorescence lines. The first began with NaCl, for which the compressibility has been determined by first principles in 1968. The major pitfall of this method of measuring pressure is that the use of X-rays is required. Many experiments do not require X-rays and this presents a major inconvenience to conduct both the intended experiment and a diffraction experiment. In 1971, the NBS high pressure group was set in pursuit of a spectroscopic method for determining pressure. It was found that the wavelength of ruby fluorescence emissions change with pressure; this was easily calibrated against the NaCl scale.
Once pressure could be generated and measured it quickly became a competition for which cells can go the highest. The need for a reliable pressure scale became more important during this race. Shock-wave data for the compressibilities of Cu, Mo, Pd, and Ag were available at this time and could be used to define equations of states up to Mbar pressure. Using these scales these pressures were reported: + Highest reported cell pressure Year Pressure 1976 1.2 Mbar (120 GPa) 1979 1.5 Mbar (150 GPa) 1985 2.5 Mbar (250 GPa) 1987 5.5 Mbar (550 GPa)
Both methods are continually refined and in use today. However, the ruby method is less reliable at high temperature. Well defined equations of state are needed when adjusting temperature and pressure, two parameters that affect the lattice parameters of materials.
Uses
Prior to the invention of the diamond anvil cell, static high-pressure apparatus required large hydraulic presses which weighed several tons and required large specialized laboratories. The simplicity and compactness of the DAC meant that it could be accommodated in a wide variety of experiments. Some contemporary DACs can easily fit into a cryostat for low-temperature measurements, and for use with a superconducting electromagnet. In addition to being hard, diamonds have the advantage of being transparent to a wide range of the electromagnetic spectrum from infrared to gamma rays, with the exception of the far ultraviolet and soft X-rays. This makes the DAC a perfect device for spectroscopic experiments and for crystallographic studies using hard X-rays.