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# 1 Introduction

## 1 Introduction

Cold samples of neutral atoms and Bose-Einstein condensates have become readily available using the techniques of laser cooling and trapping , and it has been widely recognized that cold atoms are a rich resource for experiments in quantum information science. For many proposals, however, quantum control of the atomic motional degrees of freedom is essential. For example, quantum computation in a cavity QED setting or through controlled cold collisions requires the ability to trap and control single atoms in the Lamb-Dicke regime . In 1995, Weinstein and Libbrecht noted that micron-sized wires, fabricated on a substrate, are capable of producing the large magnetic field gradients and curvatures required for trapping atoms in the Lamb-Dicke regime . Westervelt et al., in 1998, succeeded in fabricating the wire patterns used in the trap designs of Weinstein and Libbrecht . These microwire devices, now commonly known as atom chips , have been used to great success in atom optics and in the production of Bose-Einstein condensates (BEC), and are promising tools not just for quantum computation, but for atom interferometry, cavity QED, and the study of cold collisions as well. In this paper we describe techniques, which have been adapted from the standard lore of microfabrication, for fabricating this increasingly important tool for atomic physics and quantum optics.

Atom optical elements, such as mirrors, waveguides, splitters, traps, and conveyor belts have been demonstrated using atom chips . Cesium cold collisions in the presence of light have been studied using a magnetic microtrap , and the use of fiber gap  and microsphere cavities  for on-chip atom detection is being explored. Ion trap experiments are now using substrates with microfabricated electric pads for the purpose of controlling ion position .

On-chip production of a BEC has been one of the most successful uses of the atom chip thus far . Ioffe traps formed from microwires can produce extremely large trap compressions that enhance the efficiency of evaporative cooling. Consequently, condensate production time can be reduced from one minute to approximately ten seconds , and MOT loading can occur from a thermal vapor in a glass cell with a vacuum of only a few $`10^{10}`$ Torr. All of the required magnetic fields can be produced on-chip , removing the necessity of large, high power external coils. The atom chip greatly miniaturizes BEC production and will enable the integration of matter waves with chip-based atom optics and photonics.

Another exciting avenue of research involves the use of an atom chip to trap, in the Lamb-Dicke regime, one or more atoms in the mode of a high finesse cavity. The combination of magnetic microtraps and photonic bandgap (PBG) cavities would be an excellent cavity QED system for the implementation of scalable quantum computation, or for the study of continuous measurement and quantum-limited feedback. One technical proposal involves the integration of a PBG cavity with an Ioffe trap formed from microwires patterned on the same surface . The combination of small mode volume and modest optical quality factor that should be obtainable with PBG structures would enable strong atom-cavity coupling. This would be an interesting alternative to present experiments that utilize a Far Off Resonance Trap (FORT) to confine atoms inside optical Fabry-Perot cavities . Several PBG cavities, each with an independent microwire trap, could be fabricated on the same substrate and coupled together with a network of line-defect optical waveguides.

Atom chips exploit the interaction potential, $`V=\stackrel{}{\mu }\stackrel{}{B}`$, between an atom’s magnetic moment, $`\stackrel{}{\mu }`$, and a wire’s magnetic field, $`\stackrel{}{B}`$, to trap or guide weak-field seeking states of a neutral atom. In general, the field’s magnitude, gradient, and curvature scale as $`I/r`$, $`I/r^2`$, and $`I/r^3`$, respectively, where $`I`$ is the wire’s current and $`r`$ is its characteristic dimension. Microscopic wire patterns maximize field gradients and curvatures while keeping power dissipation to a minimum. Experiments involve ultra-high vacuum chambers wherein atoms are trapped and cooled near the vicinity of the atom chip’s confining magnetic potentials.

## 2 Fabrication Challenges and Constraints

Fabrication of atom chips poses several challenges in addition to those encountered in standard photolithography. Many applications require the wires to be a couple microns wide by a few microns tall and spaced only a few microns from one another. One micron resolution is near the limit of standard photolithography, and much care must be taken to accurately produce these micron-sized wires. Wires with widths much less than a micron are of limited usefulness since they become limited to the same maximum current density as micron-sized wires . Further fabrication complications arise from the need to trap the atoms near the substrate’s surface, and the need to connect the microwires to macroscopic leads without blocking optical access. A common technique for trapping atoms near the substrate surface, the mirror magneto-optical trap (MMOT), requires that this surface be an optical mirror as well as the support surface for the microwires (see figure 2. The substrate surface needs to be larger than 5 to 10 cm2 to accommodate the reflected trapping beams as well as to allow the pads for macroscopic wire contacts to be outside of the mirror area and not blocking the optical access needed for the trapping, imaging, and pumping beams. Consequently, the wire pattern must be flawless over an exceptionally large surface area: during fabrication one must be extremely careful that no dust or surface defects break or short the wires.

The major fabrication challenge lies in increasing the height of the wires to a few microns. Even the smallest wires need to support up to an amp of current, and consequently, the cross-sectional area of the wire must be maximized. This reduces wire resistance and limits the heating that causes wire breakdown. Moreover, attention must be paid to the thermal conductivity of the substrate and mounting system to ensure sufficient power dissipation. Sapphire or polished aluminum nitride (AlN) substrates provide sufficient thermal conductivity, but are slightly trickier to use for fabrication than more standard substrates.

The use of microwires to create an Ioffe trap illustrates these challenges. The wire pattern shown in figures 2(a) and (b) creates a 3D harmonic trap when combined with a perpendicular homogenous bias field . Unlike a quadrupole trap, the Ioffe trap has a non-zero field at the trap center and thus does not suffer from Majorana spin-flip losses. An atom is confined within the Lamb-Dicke regime when its recoil energy is less then the trap’s vibrational level spacing ($`\eta =(E_{recoil}/E_{vib})^{1/2}<1`$), and for a cesium atom this occurs when the trap curvature exceeds $`2\times 10^6`$ G/cm2. To achieve this extremely large field curvature in all three dimensions, the radius of the wire pattern in figure 2(a) must be smaller than $`30\mu `$m. For a trap of inner radius 10 $`\mu `$m, outer radius 15 $`\mu `$m, and wire current $`I=1`$ A, the curvature and Lamb-Dicke parameter, $`\eta `$, at the center of the trap in the axis perpendicular (plane parallel) to the substrate is $`2\times 10^8`$ G/cm2 ($`2\times 10^{10}`$ G/cm2) and $`\eta =0.38`$ ($`\eta =0.11`$). The closely spaced wires can only be a few microns wide, and even if fabricated to a height of 2 to 4 microns, the wires would need to support the large current density of $`10^{11}`$ A/m2. The accommodation of laser beams for atom cooling, loading, and imaging constrains and complicates the atom chip’s design. The trap minimum is only 7 $`\mu `$m from the substrate’s surface, and the mirror patterned on the surface for use with the MMOT must neither short the Ioffe wires nor extend more than $`5\mu `$m from the surface. The following sections describe the necessary fabrication tools and the techniques we use to overcome these challenges.

## 3 The Elements of Atom Chip Fabrication

Microfabrication is a labor intensive process, often involving several weeks of trial and error to perfect the fabrication recipe. However, once the process works, five to ten atom chips can be produced over a span of two to three days. The intent of this paper is to provide the researcher who has access to a standard clean-room enough information to design and fabricate an atom chip. We will describe the use of fabrication instruments and techniques only insofar as they are relevant to atom chips. Fabrication is not an exact science, and the techniques described here may not be optimal, but nevertheless have proven successful for the chips we have fabricated.

In photolithography, UV light shone through a photomask casts shadows onto photoresist, a light sensitive polymer, which is coated on the surface of the substrate. Either positive or negative photoresist may be used, with the primary difference being that exposed areas of positive photoresist are removed after developing whereas exposed areas remain in a process using negative photoresist. The various fabrication techniques differ in how the wire metal and photoresist are used to create the wire patterns. For instance, the wire metal may be either thermally evaporated into the trenches created in the photoresist, or grown upward trough the trenches by electroplating onto a seed metallic layer underneath the photoresist. The photoresist and unwanted metal are removed leaving only the desired wire pattern. Generally, chip fabrication consists of six steps: creating a photomask containing the desired wire pattern, using photolithography to transfer the wire pattern to photoresist on a substrate, thermally evaporating wire material, increasing the wire height, preparing the surface mirror, and making contacts to macroscopic wires. The details and exact order of these steps vary depending on the specific requirements of the microwire pattern to be fabricated. For instance, wires wider than 30 $`\mu `$m or less than one micron in height may be fabricated with a much simpler technique than thinner or taller wires. This section discusses the steps common to all techniques. Procedures required to increase the wire’s thickness pertain to individual fabrication techniques and will be discussed in the next section.

### 3.1 The photomask

The photomask is typically a 10 cm square piece of glass or transparent plastic on which is printed a positive or negative 1:1 image of the wire pattern. Wire patterns with widths or spacings less than $`30\mu `$m require a professionally made chrome mask: one in which the pattern is written with chromium on a glass plate. We have used the company Photronics, Inc. (telephone 619-992-8467) to make photomasks from AutoCAD drawings. Much care must be taken in producing the AutoCAD files since not all functions are properly converted to the company’s file format. These masks are quite expensive, costing between $600 and $800, but have sub-micron resolution and are typically shipped within a week. It is possible to purchase a laser writer to produce in-house photomasks with resolution down to 0.8 $`\mu `$m. This can be a cost effective alternative to purchasing individual masks from companies.

Many commercial printing shops are capable of printing transparencies with high enough resolution to serve as photomasks for wire patterns with features larger than $`30\mu `$m. The line edges are granular on a scale of a few microns, and the UV exposure time must be adjusted to account for the ink not being perfectly opaque. However, the one day turn-around, low cost of $`\$20`$, and ease of file preparation—only an .eps file is typically needed—make the transparency photomask quite an attractive alternative for large features.

### 3.2 The substrate

As mentioned earlier, the substrate material for the atom chip should be carefully chosen: it must be electrically insulating, highly polished, insusceptible to fractures upon localized heating, and an excellent thermal conductor. We have found that both sapphire and AlN substrates satisfy these requirements. Sapphire substrates 0.5 mm to 2 mm thick with surface areas of several cm2 may be purchased from companies such as Meller Optics, Inc. (telephone 800-821-0180) for $30 to $40 apiece. A surface quality of 80-50 scratch-dig is sufficient for fabrication. The thermal conductivity of AlN, $`170180\text{W}\text{m}^1\text{K}^1`$ at $`20^{}`$C, is $`4.5`$ times higher than that of sapphire . We measured that the max current density supported by microwires on AlN, $`2\times 10^{11}`$ A/m2, is a factor of two greater than for microwires patterned on sapphire. This was measured using electroplated gold wires of varying cross-sections patterned exactly the same way on both AlN and sapphire substrates. Specifically, we used several 3 $`\mu `$m and 20 $`\mu `$m wide wires whose heights ranged from one to three microns. The substrates were glued to room temperature copper blocks using EPO-TEK H77 (Epoxy Technology, telephone 978-667-3805), a thermally conductive epoxy.

Sapphire substrates are easier to use for fabrication because their transparency allows one to detect and avoid defects and dust during the photolithography process. Polished AlN substrates may be purchased in bulk for less than $``$ $75, and unlike sapphire, AlN substrates can be cleaved with a diamond scorer to any shape desired. The polished AlN still has a considerable amount of surface roughness—one micron wide plateaus a few hundred nanometers tall are typical—but we found that it is nevertheless possible to fabricate on this surface perfect three micron wide wires spaced less than three microns from one another. The surface bumps simply map directly onto the upper surface of the wires.

### 3.3 Substrate cleaning

Before the photolithography process may begin, the surface of the substrate must be cleaned to remove all organic material and dust. Although some of the following steps may seem unnecessary and “overkill,” investing the time to thoroughly clean minimizes the chance that after many hours of work, one discovers that a piece of dirt has broken or shorted a wire. The first step is to immerse the substrate in a beaker of “piranha etch,” sulfuric acid and hydrogen peroxide in a 10:1 volume ratio brought to 100C on a hot plate for $`5`$ min. Teflon coated, flat tipped tweezers are ideal for manipulating substrates. After the etch, the substrate should be placed in a beaker of acetone, heated again to 100C for a few minutes, and finally inserted into an ultrasound cleaner for few more minutes. In extreme cases of substrate grime, a cotton tipped dowel can be used to manually wipe away the dirt. Acetone leaves a thin film—and sometimes even particulate—when allowed to dry on a substrate’s surface. It is imperative that one spray isopropanol (IPA) onto the substrate as it is removed from the acetone bath. This rinses the surface of acetone and wets it with IPA which does not quickly dry. The substrate must then be rinsed with methanol, which is relatively clean and does not leave a film, and quickly blown dry with an air or nitrogen gun. It is crucial that the air jet is aimed almost parallel to the surface so that the methanol is blown-off rather than dried on the substrate. When done correctly, the only remaining dirt particles will be along the edge of the substrate that is downwind of the air jet, and not in the center fabrication region. If the substrate is reasonably clean after the piranha etch, then the acetone step (which may actually add some dirt particulate) may be skipped, and the substrate should instead be immersed in IPA and placed inside an ultrasound cleaner.

### 3.4 Thermal evaporation

Certain fabrication techniques, to be discussed below, require that a 100 nm metal layer be thermally evaporated before coating the surface with photoresist. We take this opportunity to discuss the thermal evaporation process. We use gold for the wires because of its high electrical conductivity, resistance to corrosion, and ease of evaporation, electroplating, and wet etching. To successfully deposit gold on a substrate’s surface, one must first evaporate a 50 Å metallic layer that promotes adhesion between the gold and the sapphire or AlN. We typically use chromium, but titanium may also be used. The magnetic effects from the thin layer of chromium are negligible. In a thermal evaporator, the substrate is mounted in a vacuum chamber facing a tungsten crucible positioned a few tens of centimeters below. The crucible, known as a boat, can hold 10 to 20 pieces of $`2`$ mm long and 0.5 mm diameter gold wire. Current flows through the boat, melting the gold and spewing it upwards toward the substrate. A calibrated crystal monitor measures the deposition rate. One to two boats are sufficient to deposit 100 to 200 nm of gold, and this costs $10 to $15 per boat. There are typically only four sets of electrical feedthroughs in the evaporator’s vacuum chamber, and to deposit more gold, one needs to bring the chamber up to atmosphere, reload the boats with gold, and pump back down to base pressure—a process that takes about an hour. The substrate mounting area allows several substrates to be coated at once. Evaporating less than 1 $`\mu `$m of gold is reasonable, but depositing more than 1 $`\mu `$m becomes too expensive and time consuming, and the quality of the gold surface begins to diminish. Moreover, the vacuum chamber eventually becomes hot which may result in the failure of the crystal monitor or the burning of photoresist.

### 3.5 Photoresist spinning and baking

Photoresist does not always adhere well to the substrate’s surface. Before coating with photoresist, the substrate should be baked on a hot plate at $`150^{}`$C for a few minutes to remove surface moisture. Hexamethyldisilazane (HMDS) should be used with sapphire substrates to promote adhesion (this is unnecessary for AlN). Only a few monolayers of HMDS are required: after baking, place the sapphire in a dish next to several drops of HMDS and cover for a few minutes. Note that both HMDS and photoresist are carcinogenic and should be handled with care.

Spinning photoresist onto a substrate is a relatively straightforward process. The substrate, with beads of photoresist dripped onto its surface, is spun by a vacuum chuck to a few thousand rpm for several tens of seconds. A faster rotation results in a thinner film of photoresist. Typically, a film thickness of a few microns is possible with standard photoresists, and there exists special resists that are four to twenty microns thick. These thick resists are often important for making tall wire structures. The thickness of a photoresist may be increased beyond its specification by dripping resist onto its surface during rotation. After spin-coating, the photoresist needs to be baked on a hot plate to prepare the polymer for UV exposure. The exact temperature and bake duration are often crucial to the success of the fabrication. We would like to note that it is possible to layer microwire patterns on top of one another by fabricating each new wire layer on top of a spin-coated insulator such as polyimide .

### 3.6 UV exposure

The central step in photolithography is the UV exposure of the photoresist. An instrument known as a mask aligner allows one to accurately position the photomask flush to the substrate’s photoresist-coated surface, and a built-in UV lamp exposes the photoresist for a specified amount of time. Essential for photomask and substrate registration is an optical microscope mounted on the mask aligner. This enables one to simultaneously view the wire patterns on the mask and the underlying substrate. Dust particles or scratches often remain on the substrate even after a thorough cleaning. If these defects are sparse, then the substrate may be translated such that the wires avoid all defects. Aligning the chip’s wire pads along one or more edges of the substrate further constrains the relative position of the photomask to the substrate. It should be noted that it is difficult to properly develop the pads (or other wire features) less than a millimeter from the edge due to photoresist beading. Certain fabrication recipes require the photoresist to be baked and exposed again before developing.

It is good practice to clean the chrome photomasks after every use. Photoresist can stick to the surface, and if left for days, will produce hard to remove specs that can block the UV light, creating unwanted features or breaks in the patterned wires. Immersing in a dish of acetone and rinsing with IPA and methanol is sufficient for routine cleaning. Some chrome masks can withstand ultrasound cleaning as well as being wiped with a soft, lint-free cloth, and this seems to be the only way to remove encrusted grime or particulate.

### 3.7 Developing

To remove the photoresist regions defined by the UV exposure, the substrate must be immersed and slightly agitated in a beaker of developer for a few tens of seconds followed by a water rinse. The exact developing time depends on the previous fabrication steps, but it is generally possible, especially with the transparent sapphire substrates, to see a characteristic change in opacity of the photoresist as it becomes fully developed. For instance, when using a positive process, one first sees the exposed photoresist turn hazy, revealing the wire pattern. After a few seconds, the hazy region sloughs off exposing the bare substrate and leaving darker, patterned regions of photoresist. If a mistake is made at any point in the photolithography process, the substrate can be reused by removing the photoresist in a beaker of acetone and cleaning the substrate as mentioned above, starting with the ultrasound.

### 3.8 Ozone dry stripping

Certain fabrication processes require the substrate surface to be etched in an ozone dry stripper. This uses UV light, ozone, and heat to remove thin films of unwanted organic material, photoresist, or HMDS that may prevent the deposition of thermally evaporated or electroplated gold.

### 3.9 Wire contacts

Wire bonding and ultrasonic fluxless soldering are useful methods for attaching macroscopic wires to the substrate’s contact pads. Wire bonding is the standard method for making contacts to micro- or nanofabricated devices. The wire bonder attaches each end of a thin thread of gold wire to a pad using a heated, ultrasonically vibrating tip. The thin wire may be stretched over several millimeters between the pad on the substrate and a pad on the substrate support structure. The pads on the support structure may then be connected to standard wire contact pins. Because the wire threads are prone to break and cannot individually support more than a few hundred mA of current, it is necessary to make several redundant bonds per pad. This process can be quite time consuming. As an alternative, ultrasonic soldering irons are capable of attaching regular wires to sapphire or AlN using fluxless solder. Attaching wires is nearly as simple as standard soldering, and the fluxless solder is vacuum compatible to at least 10-9 Torr. Unfortunately, the solder material forms mounds on the substrate’s surface that can limit optical access.

### 3.10 The mirror

Finally, we would like to discuss methods for making the atom chip’s surface mirror-like. The most straightforward method involves simply patterning gold on the entire chip’s surface except for thin, $`>10\mu `$m, wide gaps around the actual wires . This technique does not add any additional steps to the fabrication procedure, but it does increase the likelihood that surface defects will short the wires through contacts to the large mirrored areas. The mirror gaps that define the wires imprint defects onto the reflected mirror MOT beams, but we have nevertheless been able to trap more than a million cesium atoms with this less than perfect mirror. Another technique involves coating the chip’s surface with an insulator and then applying a mirror coating. For example, several layers of polymethyl methacrylate (PMMA) can be spun onto the substrate. Swabbing with acetone removes the PMMA covering the wire pads near the substrate’s edge, and the mirror is created by using a mask to thermally evaporate gold only onto the PMMA-coated region. Epoxying a silver mirror (with EPO-TEK 353) to the surface also forms a good mirror, and it eliminates any corrugations on the mirror surface caused by the underlying wires . Unfortunately, the minimum distance between the atoms and the wires is set by the mirror and epoxy thickness. An improved mirror can be made by epoxying a dialectic mirror onto the surface. Vacuums of $`2\times 10^{10}`$ Torr, in a chamber baked to 150C, have been achieved despite using this glue and dielectric coating.

## 4 Specific fabrication techniques: wet etching, ion milling, lift-off method, and electroplating

The minimum required wire dimensions vary significantly depending on the the atom chip’s application, and an optimal fabrication technique should be chosen accordingly. This section describes the recipe and relative merit of each fabrication method.

### 4.1 Wet etching and ion milling

The simplest chip to fabricate has wire widths no smaller than 30–40 $`\mu `$m and wire heights less than 1 $`\mu `$m. A transparency mask should be used for the photolithography. The wire height is set by a thermally evaporated gold layer and the photoresist masks the gold intended for wires from the wet etch solution (see figure 4.1(a)).

To begin the procedure, the cleaned substrate should be placed in the ozone dry stripper for five minutes at 65C to ensure that no organic material will prevent the adhesion of chromium and gold. The thermal evaporation step follows, with the thickness of the gold layer determined by chip’s current density requirements. Because the photoresist adheres well to gold, only a 5 min bake at 180C is necessary for adhesion. Wet etching removes exposed gold, and the photoresist should be patterned such than it covers the areas intended for wires, i.e. the photoresist should be a positive image of the wire pattern. A photomask on which the wires are opaque, used in conjunction with positive photoresist, will produce a positive image of the wire pattern. We use the photoresist AZ5214 (Clariant), which can serve as both a negative and positive photoresist depending on the bake and exposure procedure. The positive process recipe is as follows: spin coat at 5000 rpm for 50 s, bake at 95C for 2 min, expose for 10 to 20 s, and develop in AZ327 MIF (or some similar developer) for 30 s. All of the above times are approximate and will vary depending on the UV light intensity of the specific mask aligner and on various environmental conditions. It may be necessary to try various exposure and bake times to find the optimal recipe. These exposure times are based on the 16 mW/cm2 UV intensity of our mask aligner. To remove the gold not covered by photoresist, submerge the substrate in gold etch solution (Gold Etchant TFA, Transene Company, Inc., telephone 978-777-7860) for a few tens of seconds until only the dull gray of the chromium layer remains. Finally, remove the chromium layer with chrome etchant (CR-7S, Cyantek, Co., telephone 510-651-3341). Figures 4.1(a) and (b) show a substrate patterned in this manner. The wet etch dissolves the gold isotropically, and the decrease in wire width is insignificant for wires larger than 10 to 20 $`\mu `$m. Of course, transparency masks cannot be used for features smaller than a few tens of microns.

Ion milling can be useful alternative to wet etching. Instead of removing the unwanted gold with an etch solution, argon ions bombard the surface, removing the gold not covered by photoresist (see figure 4.1(b)). This method can produce very narrow features, limited only by photoresist resolution, with heights determined by the thermally evaporated gold layer. The photoresist is also milled, but this is of no consequence as long as it is thicker than the gold layer. The substrate may become quite hot during the ion etching, and one needs to be careful that the substrate does not overheat, causing the photoresist to become hard and difficult to remove. We have used ion milling to make atom chips as well as to etch a common hard drive for use as a magnetic atom mirror .

### 4.2 The lift-off method

The quick and easy wet etch technique is unfortunately not suitable for wire widths smaller than 10 $`\mu `$m, and ion milling machines are not readily available. The lift-off method should be used for the case in which the wires need not be taller than 1 $`\mu `$m but less than 10 $`\mu `$m wide. In contrast to the wet etch technique, the photoresist in this method is used as a mask for the deposition of thermally evaporated gold. Trenches are created in a negative photoresist using a photomask with opaque wires, and evaporated gold deposits both into the trenches, adhering to the substrate, and onto the surface of the photoresist (see figure 4.1(c)). If done properly, the walls of the trenches have an overhang—which looks like an undercut when viewed from above—that prevents the unwanted gold on the photoresist from connecting to the gold in the trenches. An acetone bath dissolves the photoresist, allowing the unwanted gold to lift-off leaving the wire pattern formed from the gold in the trenches.

After cleaning the substrate, the AZ5214 is spun on the substrate for 45 s at 5000 rpm. The maximum height of the thermally evaporated wires is set by the thickness of the photoresist since lift-off will not work once the top of the gold connects with the gold on the overhang. We have been able to achieve lift-off with wires 1.5 $`\mu `$m tall by spinning the photoresist on at 2000 rpm and thermally evaporating many boats of gold over a period of three to four hours. The photoresist should then be baked for 45 s at 100C, UV exposed with the photomask for 10 s, baked again for 45 s at 123C, UV exposed with no mask for 2.1 min, and developed for 25 to 35 s. Developing is finished when one can see the wire pattern in the photoresist. A successful undercut can be seen in a microscope as a bright outline of the edges of the trenches. Before thermal evaporation, the substrate should be placed in the ozone dry stripper at 65C for 5 minutes. To promote lift-off, the acetone bath should be heated on a hot plate, and the substrate, while inside the beaker, should be sprayed with an acetone squirt bottle. It is very important that all of the gold-coated photoresist be pealed away before the substrate is removed from the acetone. Otherwise, once dried, the unwanted gold flakes become extremely difficult to separate from the surface. Difficulty in achieving lift-off may be overcome by briefly exposing the substrate to ultrasound. This is risky, however, since the gold wires might be stripped-off as well. Figure 2(b) shows an atom chip fabricated with the lift-off method.

### 4.3 Electroplating

The above methods rely on thermal evaporation to achieve the required wire thickness. This limits the wire heights to $`1\mu `$m. Electroplating the wires can increase the wire height considerably: for example, we have made 3 $`\mu `$m wide wires, 4 $`\mu `$m tall. Thick photoresist spun and patterned on a thin gold seed layer provide a template for the growth of the wires. The walls of the photoresist maintain a constant wire width as the wire height increases (see figure 4.1(d)). An acetone wash followed by a brief wet etch removes the photoresist and gold seed layer. Electroplating is a tricky process that does not always produce reliable results. We provide here a general guideline for the process, and with this process we have typically been able to achieve a 75% yield with a wire height accuracy of $`\pm 0.5\mu `$m.

Fabrication begins with cleaning and ozone dry stripping the substrate, followed by the thermal evaporation of a 100 to 150 nm seed layer of gold along with a 50 Å chromium adhesion layer. For proper wire guiding, the photoresist must always be taller than the electroplated wires, and a photoresist thicker than the one used in the aforementioned techniques is necessary. Clariant’s AZ9200 series photoresists are 4 to 24 microns thick, and can achieve aspect ratios of 5 to 7 with resolutions of $`<1\mu `$m to 3.5 $`\mu `$m depending on the resist thickness. After spin coating, the photoresist should be UV exposed for 60 s (or longer depending on the photoresist thickness) using a photomask with transparent wire patterns. The resist is developed in a 1:4 solution of AZ400K and water for a minute or more: the exposed photoresist will turn hazy before dissolving away. The gold seed layer also acts as the cathode in the electroplating process, and some of the photoresist must be whipped away with acetone—or a blank spot designed in the photoresist—to serve as a contact for the cathode lead. An ozone dry etch is then used to remove any layers of HMDS, photoresist, or organics that might mask regions of the gold from the electroplating solution. The time and temperature of this process is crucial: too long of an exposure at too high of a temperature will make the photoresist difficult to remove between closely spaced wires, and too short of an exposure will not remove enough unwanted masking material. For example, we found that an 18 s room-temperature ozone dry etch was optimal for removing unwanted material while also enabling the removal of photoresist between wires spaced by 3 $`\mu `$m.

We use a sodium gold sulfite solution (TG-25E, Technic, Inc. telephone 714-632-0200) for the electroplating. The solution is temperature controlled on a hot plate to 60C and agitated with a magnetic stirrer. The anode is a platinum foil, and the substrate is connected to the power supply with a standard mini alligator clip. This clip can be dipped into the bath to enable the complete submersion of the substrate. We usually use a current of 0.1 to 0.2 mA to electroplate. Higher currents seem to produce rougher wire surfaces. The solution should remain clear to slightly yellowish during the process, and something is wrong if the solution starts to turn brown. The substrate should be gently agitated while electroplating to promote even plating and suppress the formation of $`5`$ $`\mu `$m tall towers of gold. Typically, it takes 10 to 30 minutes to electroplate several microns of gold at this current setting.

After electroplating, the photoresist should be removed in a room-temperature acetone bath. Sometimes it is difficult to remove the photoresist between wires spaced only several microns from one another, and in these cases the substrate—while in the acetone—should be placed in an ultrasound for a few minutes. The gold should not peel away since it is attached to the entire substrate surface. After rinsing the acetone away with IPA and methanol, the gold seed layer is removed with a $``$ 15 s wet etch. The chromium adhesion layer should also be wet etched away. Occasionally, the air jet does not remove all of the methanol from the substrate, and tiny drops of methanol can sometimes dry on leeward side of the wires. This dried methanol acts as a mask for the gold etch, leaving small puddles of the seed layer that can short adjacent wires. These puddles can be removed by rinsing with methanol, blow-drying from a different angle, and briefly wet etching a second time. The surface reflectance of the gold is typically diminished after the wet etch, and a mirror fabricated with this gold may not be ideal.

A surface profilometer, commonly known as an alpha step machine, is quite useful for quickly measuring the height of the wires. Inevitably, a few substrates must be spent optimizing the electroplating process for a specific wire height. Figures 4.3(a) and (b) show an atom chip-based BEC interferometer that we fabricated by electroplating on an AlN substrate . The smallest features are five, 1 mm long wires that are each 3 $`\mu `$m wide, 4 $`\mu `$m tall, and spaced less than 3 $`\mu `$m from one another.

## 5 Conclusion

The techniques described in this paper provide a basic starting point for the design and fabrication of these atom chips. The precise control of atomic position enabled by these chips is quite crucial to many areas of research. Moreover, these devices allow an incredible miniaturization of experimenters involving cold atoms. From constructing atom optical elements to studies of BECs and cavity QED, atom chips are proving invaluable to the fields of atomic physics, quantum optics, and quantum computation.

Acknowledgements

We would like to thank Michael Roukes and Axel Scherer for use of their clean room facilities. Eyal Buks and Darrell Harrington were invaluable in teaching us the basics of photolithography. We also thank Marko Loncar for instruction in ion milling, and Jakob Reichel and Chungsok Lee for their advice regarding electroplating. This work was performed in the group of Hideo Mabuchi and supported by the Multidisciplinary University Research Initiative program under Grant No. DAAD19-00-1-0374.

References


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# Errata: Diffusion Monte Carlo study of circular quantum dots [Phys. Rev. B 62, 8120 (2000)]

Several of the energies in Tables I and II are incorrect. Most of the errors are due to incorrectly inputting the symmetry of some of the states, others are due to incorrectly converting or transcribing the energies. In particular, for $`N=4`$ we had a near degeneracy and a violation of Hund’s first rule. The corrected result has $`|L=0,S=1`$ as the ground state, as predicted by Hund’s rule. Hund’s first rule is satisfied for all $`N`$ for the confining potential used, but there is a near degeneracy for $`N=10`$. We present corrected versions of Tables I and II. All quantum Monte Carlo results have been recomputed with an improved Jastrow factor. All LSDA values in Table II have also been recalculated. The rms fluctuations of the local energy in VMC range from 0.008 H for $`N=2`$ to 0.24 H for the $`N=13`$, $`|L=1,S=1/2`$ state. The number of determinants, $`N_{\mathrm{det}}`$, in the wave functions depends on whether real or complex orbitals are employed. The values shown in Table I are for real orbitals. Not only the DMC energies, but also the VMC energies computed with LSDA and LDA orbitals agree within 1 mH in all cases tested. All LSDA values in Table II have also been recalculated. The effective Bohr radius $`a_0^{}`$ should be 97.9373 Å, rather than 97.93 Å.


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# Self Consistent Molecular Field Theory for Packing in Classical Liquids

## I Introduction

The disordered packing of molecules at liquid densities is a primary and difficult problem in the theory of liquids Widom (1967); Chandler et al. (1983). This problem is typically addressed first by consideration of model intermolecular interactions of hard-core type, interactions that rigidly exclude molecular overlap. For those systems, a quantity of primary interest is then Boltzmann’s *available phase space* Stell (1985) from which follows the thermodynamic excess chemical potential discussed here. Sophisticated theories, even if esoteric, are available Reiss et al. (1959); Wertheim (1963); Thiele (1963); Reiss (1977) for the equation of state of the hard sphere fluid. In conjunction with simulation results, adaptations of those theories provide empirically exact results for the hard sphere system Hansen and McDonald (1991). Recent theoretical activity Crooks and Chandler (1997); Chen and Weeks (2003) on the hard sphere fluid emphasizes that physical clarity is an important quality of theories that might be transplanted to describe more realistic solution models. The physical content of available models of packing of more realistically shaped molecules is conceptually similar to theories of the hard sphere fluid, but the resultant theories are naturally more complicated than for hard spheres; Refs. Boublik (1975); Reiss and Merry (1981); Wertheim (1994); Labik et al. (1995); Lee (1995); Lue and Blankschtein (1995); Mehta and Honnell (1996a, b); Barrio and Solana (1998); Largo and Solana (1999); Ben-Amotz and Omelyan (2000); Jaffer et al. (2001); Boublik (2002); Bjorling et al. (1999); Crooks and Chandler (1997) give examples of that ongoing activity.

Recent developments of a quasi-chemical approach to the theory of molecular solutions Paulaitis and Pratt (2002) have brought a new set of concepts to bear on these problems Pratt et al. (2001); these developments suggest theories with clear physical content and a clear path for progressive improvement. This paper pursues these developments further, proposing and testing a self consistent molecular field theory for molecular scale packing. More important than the specific packing problem considered here, these self consistent molecular field ideas will be carried forward to develop quasi-chemical treatments of realistic solutions Paulaitis and Pratt (2002).

## II Theory

For economy of the presentation, we specifically discuss the one component hard sphere fluid. The quasi-chemical theory is built upon the relations Pratt et al. (2001); Paulaitis and Pratt (2002)

$`p_n(R)={\displaystyle \frac{K_n(R)\rho ^n}{1+\underset{m1}{}K_m(R)\rho ^m}}`$ (1)
where $`p_n(R)`$ are probabilities for observing $`n`$ sphere centers in an observation sphere of radius $`R`$ in the liquid, and the $`K_n(R)`$ are well defined equilibrium ratios of concentrations of hard sphere $`n`$-complexes with that observation sphere with $`K_0`$ 1. The quantities $`K_n(R)`$ describe occupancy transformations fully involving the solution neighborhood of the observation volume. Except in the limit of low density, these coefficients are known only approximately. Therefore, physically motivated approximations are required to proceed to specific quantitative predictions.

Our previous study of this problem Pratt et al. (2001) identified a primitive quasi-chemical approximation in which

$`K_n(R)`$ $``$ $`{\displaystyle \frac{\zeta ^n}{n!}}{\displaystyle \underset{v}{}}𝑑𝒓_1\mathrm{}{\displaystyle \underset{v}{}}𝑑𝒓_n\mathrm{e}^{\underset{i>j=1}{\overset{n}{}}\beta u(𝒓_{ij})}.`$ (2)
Here $`v=4\pi R^3/3`$ is the volume of the observation sphere, $`\beta ^1`$ = $`kT`$, $`u(𝒓_{ij})`$ is the interaction between molecules $`i`$ and $`j`$ (the hard sphere interaction in the present case), and $`\zeta `$ is a Lagrange multiplier used to achieve consistency between the known bulk density, $`\rho `$ , and the average density in the observation volume. Because of the explicit factors of $`\rho `$ in Eq. 1, $`\zeta `$ will approach the thermodynamic excess activity, $`\mathrm{ln}\zeta =\beta \mu ^{ex}`$ with $`\mu ^{ex}`$ the excess chemical potential of Gibbs. The integrals of Eq. 2 are few-body integrals that can be estimated by Monte Carlo methods Pratt et al. (2001). A natural extension of this idea is to approximate $`K_n(R)`$ on the basis of $`n`$-molecule configurational integrals that give the low-density limiting quantity, but with inclusion of a molecular field $`\beta \phi _{SCF}(𝒓)`$ as

$`K_n(R)`$ $``$ $`{\displaystyle \frac{\zeta ^n}{n!}}{\displaystyle \underset{v}{}}𝑑𝒓_1\mathrm{}{\displaystyle \underset{v}{}}𝑑𝒓_n\mathrm{e}^{\underset{i=1}{\overset{n}{}}\beta \phi _{SCF}(𝒓_i)\underset{i>j=1}{\overset{n}{}}\beta u(𝒓_{ij})}`$ (3)
$``$ $`K_n^{(0)}(R;\beta \phi _{SCF}).`$
We will adopt the convention that the molecular field $`\beta \phi _{SCF}(𝒓)`$ be zero at the center of the observation volume, and an additive constant be absorbed in the Lagrange multipliers of the $`K_n^{(0)}(R;\beta \phi _{SCF})`$. The molecular field $`\beta \phi _{SCF}(𝒓)`$, together with the Lagrange multiplier, may be made consistent with the information that the prescribed density of the liquid is uniform within the observation volume. The density profile for the $`n`$-molecule case is Hansen and McDonald (1976)

$`\rho _n(𝒓)={\displaystyle \frac{\delta \mathrm{ln}K_n^{(0)}(R;\beta \phi _{SCF})}{\delta \beta \phi _{SCF}(𝒓)}}`$ (4)
inside the observation volume. Averaging of these profiles with respect to the possible occupancies predicts the observed density. The consistency sought is then uniformity of the density,

$`{\displaystyle \underset{m}{}}p_m{\displaystyle \frac{\delta \mathrm{ln}K_m^{(0)}(R;\beta \phi _{SCF})}{\delta \beta \phi _{SCF}(𝒓)}}={\displaystyle \frac{\delta \mathrm{ln}p_0}{\delta \beta \phi _{SCF}(𝒓)}}`$
$`={\displaystyle \frac{\delta \beta \mu ^{ex}}{\delta \beta \phi _{SCF}(𝒓)}}=\rho ,`$ (5)
for $`𝒓`$ inside the observation volume. $`p_0`$ is defined by Eq. 1, and in Eq. 5 we have noted that, for hard-core solutes, the interaction contribution to the chemical is $`\beta \mu ^{ex}`$ = -$`\mathrm{ln}p_0`$ Pratt et al. (2001); Paulaitis and Pratt (2002).

Examples of the results following from these ideas are shown in Figs. 1-5. These results were obtained from a two step iterative procedure from a starting guess $`\beta \phi _{SCF}(𝒓)`$ = 0 and the probabilities $`p_n`$ of the primitive quasi-chemical theory Pratt et al. (2001). With the current approximate results, we performed Monte Carlo calculations to estimate the densities for each occupancy, and on that basis the average density implied by the current field. We then updated the molecular field according to

$`\left[\beta \phi (𝒓)_{SCF}\right]_{new}=\left[\beta \phi (𝒓)_{SCF}\right]_{old}+f\mathrm{ln}\left[{\displaystyle \frac{\rho (r)}{\rho }}\right],`$ (6)
where $`f`$ is a constant less than one that ensures stable convergence of the molecular field; a value of 0.2 was found to work here. Convergence is obtained in 20 iterations of this procedure, typically. Using the field obtained above, we then updated the occupancies, reevaluating the $`K_n^{(0)}(R;\beta \phi _{SCF})`$ by performing additional few-body simulations to evaluate the work associated with turning on the molecular field using thermodynamic integration

$`{\displaystyle \frac{K_n^{(0)}(R;\beta \phi _{SCF})}{K_n^{(0)}(R;0)}}=\mathrm{e}^{_0^1_{j=1}^n\beta \phi _{SCF}(𝒓_j)_\lambda d\lambda }`$
where $`\lambda `$ is a coupling parameter, and $`\mathrm{}_\lambda `$ indicates averaging over configurations generated under the influence of the molecular field scaled as $`\lambda \beta \phi _{SCF}(𝒓)`$. Using these recalculated $`K_n^{(0)}(R;\beta \phi _{SCF})`$, we generated a new set of $`p_n`$, tested for convergence, and so on. This process was found to converge within two steps even at the highest densities considered. We attribute the observed convergence to the fact that the starting point, the primitive quasi-chemical theory, is accurate for the probable occupancies. The molecular fields obtained using this method were found to converge stably with little difficulty.

Fig. 1 shows the self consistent molecular fields obtained using the procedure described above up to fluid densities of $`\rho d^3`$ = 0.9, just below the hard sphere freezing transition. $`\beta \phi _{SCF}(𝒓)`$ is a monotonically increasing function of radial position from the center of the stencil volume to its boundary. This reflects the fact that in the absence of the molecular field the hard sphere particles tend to build up on the surface of the stencil volume to minimize their interactions with the other particles (Fig. 2). The molecular field makes the boundary repulsive, depletes the surface density, and homogenizes the density within the volume. The magnitude of this repulsive field increases with increasing fluid density.

The predicted hard sphere chemical potentials as a function of density using the primitive and self consistent molecular field quasi-chemical theories are compared to the chemical potential from the Carnahan-Starling equation in Fig. 3. The primitive theory works well up to $`\rho d^3`$ 0.35, roughly the critical density for Ar and the density region suggested to mark qualitative packing changes in the hard sphere fluid Giaquinta and Giunta (1987); at higher densities the primitive quasi-chemical theory systematically under-predicts the hard sphere chemical potential. The present self consistent molecular field theory significantly improves the agreement with the Carnahan-Starling equation over the entire density range. Above densities of $`\rho d^3`$ 0.6, the self consistent molecular field theory begins to over-predict the hard sphere chemical potential, though the absolute value of the error is in marked improvement over the primitive theory. We note that the self consistent molecular field theory is in closer agreement with the scaled particle (or Percus-Yevick compressibility) theory for the chemical potential.

Fig. 4 shows that the most important deficiencies of the primitive quasi-chemical theory are corrected by the self-consistent molecular field theory. Note that the self-consistent molecular field theory captures the *break-away* at high density of $`\mathrm{ln}p_0`$ from the primitive quasi-chemical prediction.

In addition to achieving a uniform density across the observation volume, the self consistent molecular field also nearly achieves thermodynamic consistency for the chemical potential. With the choice of an additive constant which makes $`\beta \phi _{SCF}(𝒓)`$ zero in the deepest interior of the observation volume, $`\mathrm{ln}\zeta `$ should approach the excess activity of the solvent in the limit of a large observation volume. We expect on a physical basis that $`\beta \phi _{SCF}(𝒓)`$ describes an interaction between the interior and the exterior of the observation volume across the intervening surface. Particularly in the present case of short ranged interactions, we expect spatial variation of $`\beta \phi _{SCF}(𝒓)`$ to be confined to a surface region. Though a stencil volume of radius $`R=d`$ is evidently not large enough to observe that bulk behavior (Fig. 1), for that $`R=d`$ case we can compare the computed excess chemical potential with the solvent activity. Fig. 5 compares -$`\mathrm{ln}p_0`$ and $`\mathrm{ln}\zeta `$ as determined by the primitive and self consistent molecular field quasi-chemical theories. While the activity evaluated within the primitive theory significantly under-predicts $`p_0`$, with the self consistent molecular field theory $`\mathrm{ln}\zeta `$ and -$`\mathrm{ln}p_0`$ agree nearly perfectly. At the highest densities, there is a slight disparity between these two quantities, and the calculated values for $`\mathrm{ln}\zeta `$ are in better agreement with the empirically known $`\beta \mu ^{ex}`$ for the hard sphere fluid.

## III Variation with Cavity Size

The related quantity

$`4\pi \rho R^2G(R)`$ $`=`$ $`{\displaystyle \frac{\mathrm{d}\mathrm{ln}p_0}{\mathrm{d}R}}`$ (8)
is of special interest in the theory of the hard sphere fluid, and of solubility more generally Stillinger (1973); Reiss (1977); Ashbaugh and Pratt (2003). In the present quasi-chemical approximation, this is

$`4\pi \rho R^2G(R)`$ $`{\displaystyle \underset{m}{}}p_m\left(\mathrm{d}\mathrm{ln}K_m(R;\beta \phi _{SCF})/\mathrm{d}R\right).`$ (9)
To analyze the required derivative, we consider that the radius $`R`$ is defined in the first place by a bare field $`\beta \phi _0`$ that is zero (0) inside the observation volume and $`\mathrm{}`$ outside. Then the full field encountered with the integrals Eq. 3 is $`\beta \phi `$ = $`\beta \phi _0`$ \+ $`\beta \phi _{SCF}`$. The result now corresponding to Eq. 4 is

$`{\displaystyle \frac{\mathrm{d}\mathrm{ln}K_m(R;\beta \phi _{SCF})}{\mathrm{d}R}}={\displaystyle _v}\rho _m(𝒓;\beta \phi _{SCF}){\displaystyle \frac{\beta \phi (𝒓)}{R}}\mathrm{d}^3r.`$
(10)
Upon separating the contribution from $`\beta \phi _0`$ and performing the population averaging, this produces the simple relation

$`4\pi \rho R^2G(R)=4\pi R^2\rho {\displaystyle _v}{\displaystyle \frac{\beta \phi _{SCF}(𝒓)}{R}}\rho \mathrm{d}^3r.`$ (11)
With this first population averaging, we emphasize that $`\beta \phi _{SCF}(𝒓)`$ doesn’t depend on the occupancy index $`m`$. The radius derivative $`\beta \phi (𝒓)/R`$ of the full field can be described by a simple formal relation. The relation

$`{\displaystyle \frac{\delta \rho _m(𝒓)}{\delta \beta \phi (𝒓^{})}}=\delta \rho _m(𝒓)\delta \rho _m(𝒓^{})`$ (12)
follows from Eq. 4 for each occupancy. Performing the population averaging at this stage, we write

$`{\displaystyle \frac{\delta \rho (𝒓)}{\delta \beta \phi (𝒓^{})}}=\delta \rho (𝒓)\delta \rho (𝒓^{})\chi (𝒓,𝒓^{})`$ (13)
and

$`\delta \beta \phi (𝒓)={\displaystyle \chi ^1(𝒓,𝒓^{})\delta \rho (𝒓^{})\mathrm{d}^3r^{}}.`$ (14)
Averaging of the functional derivative Eq. 12 *before* composing Eq. 14 is suggestive of the RPA concept of exploiting an average potential in a linear response function. To use Eq. 14, consider the density change $`\delta \rho (𝒓^{})`$ corresponding to dematerialization of the uniform density in a thin shell $`(R\mathrm{\Delta }R,R)`$.

$`{\displaystyle \frac{\beta \phi (𝒓)}{R}}=R^2\rho {\displaystyle _{\left|𝒓^{}\right|=R_{}}}\chi ^1(𝒓,𝒓^{})\mathrm{d}^2\mathrm{\Omega }^{},`$ (15)
where the latter integral is over solid angles covering the surface of the ball. We introduce now $`c(𝒓,𝒓^{})`$, the Ornstein-Zernike direct correlation function defined by $`\chi ^1(𝒓,𝒓^{})`$ = $`\delta (𝒓𝒓^{})/\rho (𝒓)c(𝒓,𝒓^{})`$. We finally obtain

$`G(R)`$ $`=`$ $`1{\displaystyle _v}c(𝒓,𝒓^{}=\widehat{z}R)\rho \mathrm{d}^3r`$ (16)
within the present approximation. In the indicated integral the $`𝒓^{}`$ coordinate is pinned to the sphere surface, and $`𝒓`$ integration is over the interior of the sphere because of Eq. 10. The function $`c(𝒓,𝒓^{})`$ is the OZ direct correlation function in the field $`\beta \phi `$ including the self consistent molecular field, thus for the case of a uniform density enclosed in a sphere of radius $`R`$ with no materal outside.

It is obvious that Eq. 16 gives the corrrect answer for the case that the solvent atoms have no interaction with one another ($`c(𝒓,𝒓^{})`$= 0), and for the same reason this formula is obviously correct in the limit of zero density. That limiting result gives the second virial coefficient theory for $`\mathrm{ln}p_0`$. At the initial order in the density

$`c(𝒓,𝒓^{})=\mathrm{exp}[\beta u(𝒓,𝒓^{})]1+O(\rho ).`$ (17)
This relation in the approximate Eq. 16 leads to the correct contribution of next order in the density for $`G(R)`$, corresponding the third virial contribution to $`\mathrm{ln}p_0`$.

Exact results are also available in the case that the observation sphere is sufficiently small, $`R\frac{d}{2}`$. Then $`p_0`$ = 1-$`4\pi \rho R^3/3`$, $`\beta \phi _{SCF}(𝒓)`$=$`\mathrm{ln}\left(14\pi \rho R^3/3\right)`$ (spatially uniform in $`0rR`$, so in the formulation above this would be reflected solely in the Lagrange multipliers). Direct calculation gives $`\chi (𝒓,𝒓^{})`$ = $`\rho \delta (𝒓𝒓^{})\rho ^2`$, and $`\chi ^1(𝒓,𝒓^{})`$ = $`\rho ^1\delta (𝒓,𝒓^{})`$ \+ $`\frac{1}{14\pi \rho R^3/3}`$. Using these results in Eq. 16 gives the known answer, $`G(R)`$=$`\frac{1}{14\pi \rho R^3/3}`$. Tests of other current theories in this regime have been given by Chen and Weeks (2003).

## IV Concluding Discussion

The physical content of the present self consistent molecular field theory is simple and clear, and this theory is as accurate as the most accurate prior theories, particularly the scaled particle (Percus-Yevick compressibility) theory, for the thermodynamics of the hard sphere fluid. The conclusion is that careful attention to the near neighborhood of a distinguished solute in such a liquid, with a self consistent molecular field describing the influence of the more distant neighborhood, provides an accurate description of packing in dense liquids. Though distinct, the *hydrostatic linear response* theory Chen and Weeks (2003) leads to a similar conclusion that good theories of these phenomena can be extremely local. The present results address contributions essential to quasi-chemical descriptions of solvation in more realistic cases, as has been discussed on a conceptual basis recently Paulaitis and Pratt (2002).

The present results provide a definite, and organized basis for theoretical study of subsequent solvation phenomena. For example, consider inclusion of attractive interactions between solvent molecule spheres, interactions secondary to the repulsive interactions. The simple estimate $`c(r)\beta u(r)`$ for distances not too small, is consistent with Eq. 17. But when $`u(r)`$ at those distances describes attractive interactions, Eq. 16 then predicts that these attractive interactions reduce the magnitude of $`G(R)`$. This is a behavior that has been much discussed over recent years in the context of theories of inert gas solubility in liquid water Pratt et al. (2001); Pratt (2002); Paulaitis and Pratt (2002); Ashbaugh and Pratt (2003).

A related but distinct issue is how these packing questions are affected by multiphasic behavior of the solution, particularly the possibility of  *drying* Lum et al. (1999); Weeks (2002); Chandler (2002) or preferential absorption Diaz et al. (2002) in biophysical aqueous applications. In such cases, it is attractive to speculate that the self consistent molecular field $`\beta \phi _{SCF}`$ should reflect those multiphase possibilities just as it can in pedagogical treatments of non-molecular models of phase transitions Ma (1985).

## Acknowledgements

We thank for Dilip Asthagiri and Michael E. Paulaitis for discussions and comments on a preliminary draft of this paper. This work was supported by the US Department of Energy, contract W-7405-ENG-36, under the LDRD program at Los Alamos. LA-UR-03-3111.


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# Analogue models for FRW cosmologies

## I Motivation

It is by now well known that various condensed matter systems may be used to mimic many of the kinematic aspects of general relativity, and in particular of curved-spacetime quantum field theory unruh ; unexpected ; analog ; book . Prior work has focussed largely on black holes and event horizons, but there are also interesting cosmological issues that can be addressed. In this essay we will take a look at what would be needed to mimic a cosmological spacetime — to be precise a spatially flat FRW cosmology — in one of these analogue models. There are two quite different ways of trying to achieve the same goal:

* One might rely on an explosion, physically mimicking the big bang by an outflow of whatever medium is being used to carry the excitations of the analogue model (see e.g. FeFi ). Unfortunately, this idea appears to encounter dynamical problems in practice, problems not inherent to the type of geometry being reproduced.
* More subtly, one can avoid the need for any actual physical motion (and avoid the dynamical problems) by instead adjusting the propagation speed of the excitations in the analogue model.

The physical metric we will be trying to emulate is that of a spatially flat FRW cosmology

$$\mathrm{d}s_{\mathrm{FRW}}^2=c^2\mathrm{d}t^2+a(t)^2\mathrm{d}\stackrel{}{x}^2,$$
(1)
where $`a(t)`$ is the scale factor of the universe as a function of time. In contrast the analogue models generically provide effective metrics of the form unruh ; unexpected ; analog ; book

$$\mathrm{d}s_{\mathrm{effective}}^2=\frac{\rho (t,\stackrel{}{x})}{c_s(t,\stackrel{}{x})}\left\{[c_s^2(t,\stackrel{}{x})v^2(t,\stackrel{}{x})]\mathrm{d}t^22\stackrel{}{v}(t,\stackrel{}{x})dt\mathrm{d}\stackrel{}{x}+\mathrm{d}\stackrel{}{x}^2\right\}.$$
(2)
Here $`\stackrel{}{v}(t,\stackrel{}{x})`$ is the physical velocity of the medium, $`c_s(t,\stackrel{}{x})`$ is the propagation speed of whatever excitations we are interested in studying, and the conformal prefactor $`\rho (t,\stackrel{}{x})/c_s(t,\stackrel{}{x})`$ depends both on the dimensionality of spacetime and \[to some extent\] on the specific choice of the analogue model. In the form presented above the conformal factor is appropriate to either ordinary sound in a classical fluid unruh ; unexpected ; analog ; book , or to phonons in a BEC bec , both in (3+1) dimensions.

We now want to consider the fundamental question — given the availability of “effective metrics” of type (2), how close can one get to reproducing a FRW metric of type (1). That this question is non-vacuous can be deduced from the observation that in the black hole context “effective metrics” of type (2) never exactly reproduce the Schwarzschild geometry analog , they can do so only up to an overall conformal factor. We wish to check, in particular, if the same phenomenon shows up in a cosmological context.

## II Explosions

As mentioned in the introduction, one plausible approach is to rely on an actual physical explosion in the medium to mimic the big bang FeFi . Start with the FRW metric $`(\text{1})`$ and substitute

$$\stackrel{}{z}=b(t)\stackrel{}{x};\mathrm{d}\stackrel{}{z}=b(t)\mathrm{d}\stackrel{}{x}+\dot{b}(t)\stackrel{}{x}\mathrm{d}t;b(t)\mathrm{d}\stackrel{}{x}=\mathrm{d}\stackrel{}{z}\frac{\dot{b}(t)}{b(t)}\stackrel{}{z}\mathrm{d}t;$$
(3)
Then, introducing a Hubble-like parameter,

$$H_b(t)=\frac{\dot{b}(t)}{b(t)},$$
(4)
the FRW metric $`(\text{1})`$ is transformed to

$$\mathrm{d}s_{\mathrm{FRW}}^2=\left[c^2\frac{a^2}{b^2}H_b(t)^2\stackrel{}{z}^2\right]\mathrm{d}t^22\frac{a^2}{b^2}H_b(t)\stackrel{}{z}\mathrm{d}\stackrel{}{z}\mathrm{d}t+\frac{a^2}{b^2}\mathrm{d}\stackrel{}{z}^2.$$
(5)
This metric is equivalent to the required “effective metric” form \[equation $`(\text{2})`$\], provided we take

$$\stackrel{}{v}(t,\stackrel{}{z})H_b(t)\stackrel{}{z};c_s\frac{b}{a}c;\frac{\rho }{c_s}\frac{a^2}{b^2}.$$
(6)
The continuity equation for the medium,

$$\dot{\rho }+\stackrel{}{}(\rho \stackrel{}{v})=0,$$
(7)
particularized to the flow field $`\stackrel{}{v}(t,\stackrel{}{z})H_b(t)\stackrel{}{z}`$ implies

$$\dot{\rho }+3\rho H_b(t)=0;\rho (t)\frac{1}{b^3(t)}.$$
(8)
Using the last equivalence in Eq. (6) we can now fix the behaviour of $`c_s(t)`$ as a function of $`a(t)`$ and $`b(t)`$

$$c_s(t)\frac{1}{a(t)^2b(t)}.$$
(9)
Equations (8) and (9), together with the first equivalence in Eq. (6), completely fix the relation between the hydrodynamical quantities $`(\rho (t),\stackrel{}{v}(t,\stackrel{}{z}),c_s(t))`$ and the cosmological solution parameters $`(a(t),b(t),c)`$.

Although the “explosion route” just discussed seems promising, one should note that because of the linearly rising velocity field $`\stackrel{}{v}=H_b\stackrel{}{z}`$, this particular realization of a FRW effective geometry is guaranteed to possess an apparent horizon, a spherical surface in which the speed of the fluid surpasses the speed of sound. From a dynamical point of view, this might introduce many practical problems not intrinsically inherent to the type of geometries we are trying to reproduce. In this sense, we view the use of an exploding medium as not being a particularly useful analogue for an expanding FRW universe.

## III Varying propagation speed

A much better analogue of an expanding FRW universe can be obtained by keeping the medium at rest and instead varying the propagation speed of the excitations. In this case the continuity equation implies that $`\rho (t,\stackrel{}{x})`$ is a constant, so that we can rescale the metric by a constant factor $`c_0/\rho `$ (where $`c_0`$ is any convenient reference speed) obtaining

$$\mathrm{d}s_{\mathrm{effective}}^2=\frac{c_0}{c_s(t)}\left\{c_s^2(t)\mathrm{d}t^2+\mathrm{d}\stackrel{}{x}^2\right\}=c_0c_s(t)\mathrm{d}t^2+\frac{c_0}{c_s(t)}\mathrm{d}\stackrel{}{x}^2.$$
(10)
Now introduce a pseudo-time $`\tau `$, related to laboratory time via $`\mathrm{d}\tau =\mathrm{d}t\sqrt{c_s(t)/c_0}`$. Then

$$\mathrm{d}s_{\mathrm{effective}}^2=c_0^2\mathrm{d}\tau ^2+\frac{c_0}{c_s(t)}\mathrm{d}\stackrel{}{x}^2.$$
(11)
Consequently we completely reproduce a FRW cosmology provided we identify

$$c_0\mathrm{d}\tau c\mathrm{d}t_{\mathrm{FRW}};\frac{c_0}{c_s(t)}a(\tau )^2.$$
(12)
That is, an expanding universe corresponds in the effective geometry to a decreasing propagation speed. A tricky point is that $`c_s`$ is still presented in terms of laboratory time $`t`$ as the speed $`\mathrm{d}\stackrel{}{x}/\mathrm{d}t`$. However in terms of the pseudo-time $`\tau `$ the excitations propagate at speed

$$\overline{c}_s(\tau )=\frac{\mathrm{d}\stackrel{}{x}}{\mathrm{d}\tau }=\frac{\mathrm{d}t}{\mathrm{d}\tau }\frac{\mathrm{d}\stackrel{}{x}}{\mathrm{d}t}=\sqrt{\frac{c_0}{c_s(t)}}c_s(t)=\sqrt{c_0c_s(t)}.$$
(13)
Having obtained the general analogue of the flat FRW metric it is interesting to investigate the analogue equivalent of the inflationary solution. We can start by re-writing the analogue Hubble factor as

$$H=\frac{a^{}(\tau )}{a(\tau )}=\frac{1}{2}\sqrt{\frac{c_s}{c_0}}\dot{a}\frac{\mathrm{d}t}{\mathrm{d}\tau }=\frac{1}{2}\sqrt{\frac{c_0}{c_s}}\frac{\dot{c_s}}{c_s}.$$
(14)
where the prime represents derivative with respect to the pseudo-time and the dot with respect to the laboratory time. The inflationary solution is then easily obtained by using a exponential law in pseudo-time $`\tau `$

$$a(\tau )=e^{H\tau };a(t)=Ht;$$
(15)
corresponding to a power law in physical time for the speed of sound (measured in physical time)

$$c_s(t)=\frac{c_0}{a^2(\tau )}=\frac{c_0}{H^2t^2}.$$
(16)
In summary the nice feature of the variable propagation speed route to a FRW analogue is that it is relatively clean; there is no moving medium which might impact the physical boundaries of any experimental apparatus and one can instead focus on what we feel is the central issue — how to physically manipulate the propagation speed $`c_s`$ (or its pseudo-time equivalent $`\overline{c}_s`$).

## IV Suitable physical mechanism: Feshbach resonance in a BEC

From the preceding discussion it is clear that one attractive route to simulating a FRW cosmology in an effective geometry is by rapid manipulation of the propagation speed of whatever excitations we might wish to focus attention on. But how is that to be accomplished? There is one particular medium, currently the center of much experimental interest, for which an appropriate mechanism has been demonstrated to exist. Here we are referring tho the use of Feshbach resonances feschbach  in Bose–Einstein condensates \[BECs\].

BECs are promising analogue systems of gravity. They have been extensively studied book ; Garay1 ; bec ; laval  in relation to the possibility of simulating black hole geometries and Hawking radiation. The basic equation used in describing the condensate is the Gross-Pitaeveskii \[GP\] equation

$$\mathrm{i}\mathrm{}\frac{}{t}\psi (t,𝐱)=\left(\frac{\mathrm{}^2}{2m}^2+V_{\mathrm{ext}}(𝐱)+\kappa \left|\psi (t,𝐱)\right|^2\right)\psi (t,𝐱);\kappa =\frac{4\pi \sigma \mathrm{}^2}{m}$$
(17)
Here $`\psi (x,t)`$ is the (classical) wave function of the condensate, ($`|\psi (x,t)|^2=n=`$the particle density of the condensate), $`V_{\mathrm{ext}}`$ is the trapping potential and $`\sigma `$ is the $`s`$-wave scattering length for the atoms (which have mass $`m`$). \[Actually it is conventional to use the symbol $`a`$ for the scattering length of a BEC condensate. We adopt this unusual notation to avoid any confusion with the scale factor of the FRW metric.\] The generic analogue model can be easily be obtained by considering the propagation of excitations in the condensate. These are described by a wave function which closely resembles that of a scalar field in a curved spacetime described by the metric (2) with $`\rho `$ replaced by $`nm`$ and where $`c_s^2=\kappa n/m`$ (see bec  for a detailed derivation). The key point is that the propagation speed is proportional to the scattering length

$$c_s^2\sigma .$$
(18)
Let us now qualitatively explain we can simulate cosmological expansion within this model. We start with a condensate in a stationary state described by a constant background density in a sufficiently large volume. This is a solution of the Gross-Pitaevskii equation. For this, one needs to have a potential that reproduces a sufficiently large hard-walled box. Using a Feshbach resonance it is now possible to change at will the scattering length $`\sigma `$ in the condensate. If one now decreases the value of the scattering length in a sufficiently slow manner (the timescale will be discussed below), then at the same time the value of the speed of sound will decrease. The analysis of the previous Section then shows that this leads to an effective FRW geometry. Fluctuations of the condensate will propagate in an effective metric which is an analogue to a spatially flat FRW geometry.

A subtle point is that when the time dependence is introduced in the system by a time-varying scattering length one must be sure to work in a regime where the background configuration is “instantaneously” reacting to theses changes. Thus we must assure that the GP equation (from which the analogue gravity framework is derived) holds at each instant of time. The validity of the GP in describing the Bose-Einstein condensate is related to the validly of several crucial assumptions, generally stated to be the “mean-field” approximation and the dilute gas approximation. It is nevertheless important to note that in a dynamical situation a third approximation, which we can call “Markovian” approximation, is implicitly assumed.

The Markovian approximation is related to the fact that in dynamical situations the two-body time-dependent scattering matrix can have a complicated form due to the “memory” of the system. In these situations the system is described by a GP-like equation where the interaction term includes a “delay term” described by an integration over time. The necessary assumption in order to have a Markovian description of the dynamics (which together with the two previous approximations leads to the GP equation) is then that the timescales on which external parameters are changing are longer that the two-body collisional duration. That is, longer than the timescale over which a single interaction happens. (Reduced to the bare bones, we are asking that the scattering length does not change significantly during the period when a pair of atoms are interacting.)

We can estimate the two-body collision time by a simple calculation. All we need is the typical size of the region of strong interaction of two atoms in the condensate, and the typical speed with which they move. The first quantity can be assumed to be of the order of the Van der Waals length. This length is basically the size of the region of strong interaction: For $`r\lambda _{vdW}`$ the scattering wave function oscillates rapidly due to the strong interaction potential. In alkali ground state interactions, $`\lambda _{vdW}`$ is typically of order of few nanometers, $`\lambda _{vdW}1`$ nm.

Regarding the typical speed of the atoms, this is set by the de Broglie momentum generated by the trap confinement: $`p=h/R`$ and $`\overline{v}=p/m`$. We shall assume a trap of typical size of ten microns. For a typical Bose-Einstein condensate one then gets an interaction timescale

$$t_i=\frac{\lambda _{vdW}}{\overline{v}}=\frac{\lambda _{vdW}mR}{h}10^6\text{ s},$$
(19)
so it would appear that a microsecond is the shortest timescale allowed for the change in $`\sigma `$.

## V Analogue cosmological particle creation

Now that the above analysis has shown that there is a regime for which a varying scattering length can be used to simulate a FRW-like effective metric one may wonder about the behaviour of the fluctuations on such a time-dependent background.

The equation satisfied by the quantum fluctuations is, in the acoustic approximation (that is for long wavelengths), that of a massless scalar field over an expanding background and therefore, it will lead to cosmological pair production of particles. Interestingly it was recently demonstrated Un-Sc  that not all analogue models of gravity are suitable for simulating particle creation from the quantum vacuum. Indeed, it may happen that even if the classical equation for the perturbations on the background resembles that for a field in curved spacetime, nonetheless one might fail to mimic quantum particle creation because the commutation relations of the analogue field are not the correct one for the physical quantum field. In this regard it is useful to note that it can be explicitly shown Un-Sc  that in the case of BECs the structure of the commutator is the correct one.

We then expect to be able to produce quantum excitations with several frequencies, typically determined by the rapidity of the change in the scattering length. In particular if $`t_{\mathrm{min}}`$ is the shortest timescale over which we can physically drive the system then $`\nu _{\mathrm{peak}}1/t_{\mathrm{min}}`$ is the peak frequency of the created quasi-particles spectrum. It is also important to check that this frequency corresponds to a wavelength shorter than the physical size of the condensate $`R`$. An easy way to do this is to confront the interaction time $`t_i`$ given in Eq. (19) with the crossing time of the condensate, $`t_{\mathrm{size}}=R/c`$.

$$\frac{t_i}{t_{size}}=\frac{\lambda _{vdW}mc}{h}=\frac{2\pi \lambda _{vdW}}{\xi },$$
(20)
where we have introduced the healing length of the condensate, defined to be $`\xi =\mathrm{}/(mc_s)`$. For typical BEC system $`\xi 0.1`$$`10\mu `$m (assuming an average value of the scattering length of a few nanometers) so

$$\frac{t_i}{t_{\mathrm{size}}}10^2\text{}10^4.$$
(21)
Thus there is a viable window of timescales (for the time dependence of the scattering length) for which both the GP equation holds, and the quasi-particles produced have wavelengths shorter than the physical size of the condensate.

The possibility of simulating cosmological particle creation is a significant advance that deserves further investigation, and might be remarkably important in the future. The simulation of inflationary scenarios, and the relevant particle creation, could lead to a better understanding of the generation of primordial inflationary perturbations and their role in the generation of large scale structure. Moreover it should be noted that the quasi-particles generated in this way will be characterized by a phononic dispersion relation $`\omega ^2=c_s^2k^2`$ only at long wavelengths with respect to the healing length of the condensate. In general for wavelengths comparable with the healing length of the condensate the Bogoliubov dispersion relation

$$\omega =\sqrt{c_s^2k^2+\left(\frac{\mathrm{}}{2m}k^2\right)^2},$$
(22)
will hold broken . This is particularly interesting due to the recent intense debate about the detectability of inflationary spectrum due to these kind of dispersion relations Bran-Mart ; Pare .

## VI Conclusions and Prospects

Our major conclusions are four-fold:

* At a theoretical level, it is clear that any mechanism for changing the propagation speed in a stationary medium is from a mathematical perspective equivalent to working in an expanding (or collapsing) spatially flat FRW universe.
* At an experimental level, the use of a Feshbach resonance in a Bose–Einstein condensate yields a way of influencing the scattering length, and hence the propagation speed, without changes in condensate density — and more importantly without violating the approximations made in deriving the Gross-Pitaevskii equation on which the entire “effective metric” approach to phonon propagation in BECs is based.
* At a very practical engineering level, the relevant parameters seem to be well within our technological horizon.
* Building an analogue FRW cosmology (suitable for testing semiclassical quantum effects) seems considerably less problematic than building an analogue black hole book ; Garay1 ; laval .

In summary: The prospects for direct laboratory simulation of an expanding universe, and consequent cosmological particle production are very good. Given the relatively small number of experimental tests of curved space quantum field theory, any progress along these lines is important. Our long range goal is to turn at least some aspects of cosmology into a laboratory science, not just an observational science.