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# Self-Doping of Gold Chains on Silicon: A New Structural Model for Si(111)5×2-Au

## Abstract

A new structural model for the Si(111)5$`\times `$2-Au reconstruction is proposed and analyzed using first-principles calculations. The basic model consists of a “double honeycomb chain” decorated by Si adatoms. The 5$`\times `$1 periodicity of the honeycomb chains is doubled by the presence of a half-occupied row of Si atoms that partially rebonds the chains. Additional adatoms supply electrons that dope the parent band structure and stabilize the period doubling; the optimal doping corresponds to one adatom per four 5$`\times `$2 cells, in agreement with experiment. All the main features observed in scanning tunneling microscopy and photoemission are well reproduced.

Physical realizations of a one-dimensional metal are rare, in part because they may be preempted by a metal-insulator Peierls transition himpsel\_journal\_of\_electron\_spectroscopy\_and\_related\_phenomena\_2002a . An escape clause is available for metallic chains adsorbed on rigid substrates, however, since the energy penalty for the pairing distortion may be prohibitively high. For example, when gold is adsorbed on silicon a variety of chain-like structures are formed, some with unusual electronic properties suggestive of a one-dimensional metal segovia\_nature\_1999a ; losio\_phys\_rev\_lett\_2001a . Photoemission data from the vicinal surfaces Si(553)-Au and Si(557)-Au reveal fractionally filled bands with strongly one-dimensional character, which are believed to originate from Au “chains” just one atom wide crain\_phys\_rev\_lett\_2003a . Structural models for Si(557)-Au were recently proposed based on total-energy calculations sanchez-portal\_phys\_rev\_b\_2002a  and x-ray data robinson\_phys\_rev\_lett\_2002a .

Even more widely studied is the parent flat surface, Si(111)-Au. First reported over twenty-five years ago lipson\_j\_phys\_c\_1974a ; lelay\_surf\_sci\_1977a , the Si(111)5$`\times `$2-Au reconstruction has been extensively characterized by low-energy electron diffraction bishop\_british\_journal\_of\_applied\_physics\_1969a ; lelay\_surf\_sci\_1977a , scanning tunneling microscopy (STM) baski\_phys\_rev\_b\_1990a ; omahony\_surf\_sci\_1992a ; omahony\_phys\_rev\_b\_1994a , x-ray diffraction schamper\_phys\_rev\_b\_1991a , reflectance anisotropy spectroscopy power\_phys\_rev\_b\_1997a , angle-resolved photoemission collins\_surf\_sci\_1995a ; altmann\_phys\_rev\_b\_2001a , inverse photoemission hill\_appl\_surf\_sci\_1998a , and core-level spectroscopy zhang\_phys\_rev\_b\_2002b . Despite this scrutiny, its structure remains unknown. The data provide several constraints on any model of Si(111)5$`\times `$2-Au. (1) STM shows the surface to be decorated by bright protrusions with apparent height $``$1.5 Å and whose coverage, although variable, has a preferred value of one per 5$`\times `$8 supercell bennewitz\_nanotechnology\_2002a . (2) Away from the protrusions, STM images show a “Y”-shaped feature whose orientation is determined by the underlying lattice omahony\_surf\_sci\_1992a ; omahony\_phys\_rev\_b\_1994a ; power\_phys\_rev\_b\_1997a . (3) Photoemission finds a strong surface band beginning at the the 5$`\times `$2 zone boundary and dispersing downward toward the 5$`\times `$1 zone boundary altmann\_phys\_rev\_b\_2001a . (4) The nature of this band changes from one-dimensional at the top of the band to two-dimensional at its bottom losio\_phys\_rev\_lett\_2000a .

In this Letter a new model is proposed for Si(111)5$`\times `$2-Au that explains all of these observed features. The model is related to those proposed earlier for Si(557)-Au, suggesting that all of the reconstructions formed by adsorption of Au on Si form a family. It is also closely related to the “honeycomb chain-channel” (HCC) model now widely accepted as the structure of the adsorbate-induced induced Si(111)3$`\times `$1 and Si(111)3$`\times `$2 reconstructions erwin\_phys\_rev\_lett\_1998a , and thus helps to unify a wide class of adsorbate-induced reconstructions based on Si(111) and its vicinals. The present model achieves its stability through an unusual “self-doping” mechanism that may be relevant to other Au-induced Si reconstructions.

The model is shown in Fig. 1. The reconstruction occurs purely in the surface layer, and has the basic structure of a “double honeycomb chain” (DHC) with underlying 5$`\times `$1 periodicity. One chain is formed by hexagons of alternating Au and Si atoms, and one by hexagons of all Si (as in the HCC model). The outer Si atoms of the Au-Si chain are too far from the Si atoms in the Si chain to bond directly. As a result, two variants of the basic model are plausible. (i) The insertion of an additional “rebonding” row of Si atoms can bridge the gap between the chains, but only at the cost of overcoordinating the Si atoms in the Au-Si chain. This will be called the “5$`\times `$1 variant.” (ii) Removing every other of these rebonding Si atoms (as shown in Fig. 1) relieves the overcoordination but now leaves dangling bonds in the Si chain; this will be called the “5$`\times `$2 variant.” These two variants are very close energetically. It will be shown below that the presence of additional Si, occurring as adatoms, acts to dope the 5$`\times `$2 variant with electrons and thereby to reduce its surface energy relative to the 5$`\times `$1 variant. The optimal doping level occurs for one adatom per four 5$`\times `$2 cells, identical to the observed equilibrium adatom coverage.

First-principles total-energy calculations were used to determine the equilibrium geometries and relative surface energies of the basic model and its variants. The calculations were performed in a slab geometry with up to six layers of Si plus the reconstructed surface layer and a vacuum region of 8 Å. All atomic positions were relaxed until the total energy changed by less than 1 meV per 5$`\times `$2 cell; the bottom Si layer was passivated by hydrogen and held fixed. Total energies and forces were calculated within the generalized-gradient approximation to density-functional theory using projector-augmented-wave potentials, as implemented in vasp kresse\_phys\_rev\_b\_1993a ; kresse\_phys\_rev\_b\_1996a . The plane-wave cutoff (180 eV) and sampling (2$`\times `$4) of the surface Brillouin zone were sufficient to converge relative surface energies to within 1 meV/Å2, adequate for the comparisons presented below. All the models considered here have equal Au coverage, and hence the relative surface energies (calculated as in Ref. erwin\_phys\_rev\_lett\_1998a, ) do not require a choice of Au chemical potential. STM images were simulated using the method of Tersoff and Hamann tersoff\_phys\_rev\_b\_1985a .

Since its discovery, many structural models have been proposed for Si(111)5$`\times `$2-Au. Most of the early ones are not compatible with newer STM data, but two later models—from Marks and Plass (MP) marks\_phys\_rev\_lett\_1995a  and Hasegawa, Hosaka, and Hosoki (HHH) hasegawa\_surf\_sci\_1996a —have recently been studied theoretically kang\_surf\_sci\_2003a . Neither was found to be consistent with STM or ARPES data, despite being locally stable with nearly equal surface energies (to within 0.1 meV/Å2). The 5$`\times `$2 DHC model proposed here is more stable than the MP and HHH models by 20 meV/Å2, or 2.6 eV per 5$`\times `$2 cell. This energy difference is sufficiently large to rule out the MP and HHH models on energetic grounds alone.

Within the family of the two DHC variants described above (5$`\times `$1 versus 5$`\times `$2, each with different Si adatom coverages) the relative surface energy changes are very much smaller, of order 1 meV/Å2. This is near the limiting precision for DFT surface energies, suggesting the need for a simpler model to describe, for example, the variation of surface energy with Si adatom coverage. In the following, this model is developed by analyzing within DFT the role of the adatoms. This requires demonstrating, first, that the observed bright protrusions in STM are, in fact, Si adatoms and not something else; and second, that the adatoms indeed supply electrons, which then dope the parent band structure.

Away from the protrusions, filled-state STM images show a series of side-by-side “Y”-shaped features with 5$`\times `$2 periodicity omahony\_surf\_sci\_1992a ; omahony\_phys\_rev\_b\_1994a ; power\_phys\_rev\_b\_1997a . A simulated STM image for the 5$`\times `$2 DHC model with no adatoms is shown in Fig. 2(a). A similar feature “Y”-shaped feature is found with paired “arms,” a single “tail,” and the same crystallographic orientation as found experimentally.

To identify the bright protrusions seen in STM images, both Si and Au adatoms were considered as potential candidates. Binding energies for individual adatoms were calculated for eight possible sites on the undecorated 5$`\times `$2 surface. For Si the most favorable site is at the center of a Au-Si hexagon, as shown in Fig. 1, where the binding energy is 4.6 eV. This is much larger than the next best site (by 0.7 eV) and hence rules out other possible locations. The simulated STM image, shown in Fig. 2(b), from a 5$`\times `$4 arrangement of Si adatoms decorating these sites is in excellent agreement with the atomically resolved images of Ref. \[bennewitz\_nanotechnology\_2002a, \]. In particular, the bright spots are correctly positioned in the middle of the underlying row structures. The linescan in Fig. 2(c) shows their apparent height to be 1.5 Å, in good agreement with the results of Ref. \[bennewitz\_nanotechnology\_2002a, \]. Finally, Au adatoms can be easily ruled out as plausible candidates: although their binding energies are substantial (from 3.1 to 3.9 eV), they relax well into the surface layer and thus produce no detectable STM spot, as demonstrated in the inset to Fig. 2(b).

Photoemission data for Si(111)5$`\times `$2-Au provide a very stringent test for any structural model. For wavevectors along the chain direction, the ARPES data reveal a strong surface band beginning at the 5$`\times `$2 zone boundary (the A2 point), and dispersing downward to its minimum at the 5$`\times `$1 zone boundary (the A1 point) before turning back up altmann\_phys\_rev\_b\_2001a . The calculated electronic structure, shown in Fig. 3, reveals just such a band between A2 and A1, whose width and effective mass (0.6 eV and 0.4$`m_e`$) are in reasonably good agreement with the data (0.9 eV and 0.5$`m_e`$). Additional bands with less pronounced surface character are also found in the data, and can be tentatively identified with calculated bands marked in Fig. 3.

One remarkable feature of the ARPES results for the strong surface band is the continuous transition, within a single band, from a one-dimensional state (at the band maximum) to a two-dimensional state (at its minimum) losio\_phys\_rev\_lett\_2000a . This feature is well reproduced in the calculated band structure, expanded views of which are shown in the two small panels of Fig. 3 for wavevectors perpendicular to the chain direction. At the maximum of the strong band, near A2, the perpendicular dispersion is small (0.04 eV), while at its minimum, near A1, the perpendicular dispersion is much larger (0.10 eV). The ARPES measurements give very similar results, 0.03$`\pm `$0.03 eV and 0.14$`\pm `$0.03 eV, respectively losio\_phys\_rev\_lett\_2000a .

It is clear from Fig. 3 that the calculated electronic structure of the bare Si(111)5$`\times `$2-Au reconstruction is metallic. As suggested in Ref. \[himpsel\_journal\_of\_electron\_spectroscopy\_and\_related\_phenomena\_2002a, \], it is interesting to ask whether the addition of Si adatoms could render the system either insulating, or at least “less metallic”; whether it is energetically favorable to do so; and—if it is—whether the predicted optimal coverage of adatoms corresponds to the equilibrium coverage deduced from STM data, one per 5$`\times `$8 supercell bennewitz\_nanotechnology\_2002a . The answer to all three questions is affirmative, as shown below.

Near the Fermi level the bands are very close to one-dimensional, as discussed above. Hence, the number of additional electrons required to render the band structure (provisionally assumed to be rigid) insulating can be trivially determined from Fig. 3 to be two per 5$`\times `$2 cell. To determine what coverage of Si adatoms is required to provide two electrons per 5$`\times `$2 cell, explicit band structure calculations must be performed. For a coverage of one adatom per 5$`\times `$2 cell, the resulting band structure is insulating. This implies that the addition of one adatom to the bare 5$`\times `$2 surface creates only one additional state in the occupied manifold: two of the adatom’s valence electrons fill this state, and the other two dope the parent band structure, rendering the full system insulating. These conclusions are independent of any assumptions about the rigidity of the parent band structure. Nevertheless, it is important to note that the bands do shift quite rigidly, with only small changes of order 0.1 eV or less. For lower adatom coverages, smaller but similarly rigid shifts are expected. This transforms the determination of the optimal adatom coverage into the equivalent task of computing the optimal electron doping.

In the absence of adatoms, the DFT surface energies of the 5$`\times `$1 and 5$`\times `$2 DHC models are very close, with the 5$`\times `$1 variant preferred by less than 1 meV/Å2. Changes in the surface energy due to electron doping were modeled by calculating the DFT total energies for cells with additional electronic charge (with a compensating background charge to preserve overall neutrality, plus the standard correction to treat the resulting spurious interactions makov\_phys\_rev\_b\_1995a ). The results are shown in Fig. 4. For the 5$`\times `$1 variant, any additional electronic charge increases the surface energy above its undoped value. The 5$`\times `$2 variant behaves quite differently: its surface energy is minimized for a doping level very close to 0.5 electron per 5$`\times `$2 cell. Since each adatom was earlier shown to supply two doping electrons per 5$`\times `$2 cell, this optimal doping level can be most easily achieved with one adatom per four 5$`\times `$2 cells. Moreover, at this optimal adatom coverage the surface energy of the 5$`\times `$2 variant is lower than that of the 5$`\times `$1, suggesting that this is indeed the observed ground-state equilibrium phase oneadatom . These findings are in excellent agreement with the experimental observation that when excess Si is evaporated at low temperature onto a Si(111)5$`\times `$2-Au surface with one adatom per four 5$`\times `$2 cells, subsequent annealing at higher temperature will cause the extra Si to diffuse away and return the system to its equilibrium state.

In summary, a new structural model has been proposed for the Si(111)5$`\times `$2-Au surface, consisting of a “double honeycomb chain” reconstruction decorated by Si adatoms. Simulated STM images from this model reproduce a number of experimentally observed features, including the in-plane location and apparent height of the bright protrusions due to the adatoms, and the “Y”-shaped features seen away from these protrusions. The calculated band structure reproduces the main features of recent photoemission data, including the unusual change in dimensionality observed within the main surface band between its energy extrema. Finally, the Si adatoms act as electron donors that dope the parent 5$`\times `$2 band structure, reducing its surface energy and stabilizing it relative to other models. The optimal doping level is equivalent to one Si adatom per four 5$`\times `$2 cells, in agreement with experimental observation.

###### Acknowledgements.

Many helpful conversations with F.J. Himpsel are gratefully acknowledged. Computations were performed at the DoD Major Shared Resource Center at ASC. This work was supported by the Office of Naval Research.


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# PROJECT OF A SUPERFLUID 3HE DETECTOR FOR DIRECT DETECTION OF NON-BARYONIC DARK MATTER : MACHE3

## 1 Introduction

The estimation of cosmological parameters has reached an unprecedented level of accuracy since the new data on the cosmic microwave background , used in combination with other cosmological observations, such as the SNIa and galaxy cluster surveys. Recent results show that matter contribution to the total density of the Universe is mainly composed of non-baryonic dark matter. Supersymmetric theories generally predict this yet still not observed and mostly non-interacting matter to be composed of WIMPs, which best motivated candidate is the neutralino .

Many collaborations have developped promising detectors to hunt actively non-baryonic dark matter candidates. These new detectors have reached significant sensitivity to begin to test regions of the SUSY parameter space compatible with accelerator and cosmological constraints and improved the upper limits on scalar and axial interaction exclusion plots . Direct detection experiments present common problems such as neutron interaction and radioactive contamination of both sensitive medium and surrounding materials. Since early experimental works ,,, a superfluid $`{}_{}{}^{3}\mathrm{He}`$ detector has been proposed  for direct detection of non-baryonic dark matter search. Monte Carlo simulations have shown that a high granularity detector, a matrix of superfluid $`{}_{}{}^{3}\mathrm{He}`$ cells, would allow to reach a high rejection factor against background events, leading to a low false neutralino event rate.

## 2 MACHe3 project

### 2.1 Superfluid $`{}_{}{}^{3}\mathrm{He}`$-B as a privileged sensitive medium

At ultra-low temperature ($``$ 100 $`\mu `$K), $`{}_{}{}^{3}\mathrm{He}`$ is a very interesting medium since it could be used as a highly sensitive bolometer. As a matter of fact, around 100 $`\mu `$K and at low pressure, $`{}_{}{}^{3}\mathrm{He}`$ is in its superfluid B phase which has an extremely small quasiparticle gap. The use of superfluid $`{}_{}{}^{3}\mathrm{He}`$-B is motivated by its very appealing features compared to other materials :

* $`{}_{}{}^{3}\mathrm{He}`$ being a 1/2 spin nucleus, will be mainly sensitive to axial interaction, making this detector complementary to existing ones, mainly sensitive to the scalar interaction. The axial interaction is largely dominant in all the SUSY region associated with a substantial elastic cross-section .
* An ultra-high purity due to its superfluid phase, only $`{}_{}{}^{4}\mathrm{He}`$ can be dissolved in superfluid $`{}_{}{}^{3}\mathrm{He}`$ but in an extremely low fraction .
* A high neutron capture cross-section ($``$10 barns for 10 keV neutrons), implying a clear signature well discriminated from a WIMP signal.
* Low Compton cross-section. No intrinsic X-rays.
* A low detection threshold, less than 1 keV.
* A high signal to noise ratio, due to the small energy range expected for a WIMP signal. The maximum recoil energy does only slightly depend on the WIMP mass, given that the target nucleus ($`\mathrm{m}_{{}_{}{}^{3}\mathrm{He}}=\mathrm{\hspace{0.17em}2.81}\mathrm{GeV}/\mathrm{c}^2`$) is much lighter than the incoming $`\stackrel{~}{\chi }`$ ($`\mathrm{M}_\chi 32\mathrm{GeV}/c^2`$). As a matter of fact, the recoil energy range needs to be studied only below $`6\mathrm{keV}`$, see .

### 2.2 A high granularity matrix

MACHe3 project will consist of a 10 kg matrix composed of 1000 cells of 125 cm3 filled with superfluid $`{}_{}{}^{3}\mathrm{He}`$ at 100 $`\mu `$K. A privileged design is shown on figure 1. It is based on a hexagonal matrix with a close to a bee nest configuration. Each cylinder is divided in 10 Lancaster type  cylindric bolometer cells. Rejection principle relies on the energy release measurement and the correlation among the cells to discriminate background events (neutrons, $`\gamma `$-rays and muons) from neutralino signal. It allows to reject background events given the fact that a WIMP fires only one cell with an energy release below 6 keV. The high granularity combined with energy deposit allows to obtain relatively good rejection as seen on figure 2. For 2.6 MeV gammas, only one over 5000 mimicks a WIMP event, meaning that 99.98% are rejected. Concerning neutrons, we benefit from the high neutron capture cross-section. The capture process, $`\mathrm{n}+{}_{}{}^{3}\mathrm{He}\mathrm{p}+^3\mathrm{H}+764\mathrm{KeV}`$, releases 764 keV in one cell. It allows to reach a very good rejection, 99.90% of 1 MeV neutrons are rejected . In underground environnement, the false event rate is estimated to be less than $``$10-1 day-1 for neutrons and $``$10-2 day-1 for muons .

### 2.3 Experimental results on a prototype cell

The elementary component of MACHe3 is the superfluid $`{}_{}{}^{3}\mathrm{He}`$ cell . An experimental test of a small prototype cell has been done with a lead shielding around the cryostat to estimate the contribution of the external natural radioactivity. The cell was a copper cylindric box ($`\mathrm{V}75\mathrm{mm}^3`$) filled with superfluid $`{}_{}{}^{3}\mathrm{He}`$ around 100 $`\mu K`$. The detection principle relies on the damping on the vibrating wire resonance. More precisely, the vibration amplitude decreases when a particle interacts inside the cell. The thermal diffusion is done through the hole. See  for more details.

Stability in temperature for one week per cycle at T $`\mathrm{\hspace{0.17em}100}\mu K`$ and detection threshold around 1 keV have been obtained. An experiment with an Am-Be neutron source has been performed to validate the response of the cell to neutron irradiation. The capture has been observed . A 14% of the total energy released by the capture is lost in scintillation and vortex production. To disentangle these effects, development of a new prototype cell with an additional signal from the temperature change of the cell walls is in progress. The detection of cosmic muons during 12 hours has been highlighted as displayed on figure 3. Experimental data exhibits a peak at 52 keV. A Geant4  simulation reproducing the experimental set-up has been developped to estimate the released energy by 2 GeV muons crossing through the cell. Simulation presents a clear peak at 67 keV. A shift compared with expectation value is observed. The energy loss may be related to UV photon emission and vortex formation .

## 3 Phenomenological study

A phenomenological study has been done with the DarkSUSY code111The version used is 3.14.01, with correction of some minor bugs. , to test performance of MACHe3 and its complementarity with existing detectors within the framework of a phenomenological supersymmetric model. A scan on a large range of all free parameters has been done, corresponding to a total number of $`2\times 10^6`$ models. Accelerator constraints as well as cosmological ones have been considered .

Using the DarkSUSY code, the $`\stackrel{~}{\chi }`$ -$`{}_{}{}^{3}\mathrm{He}`$ axial cross-section has been evaluated. The $`\stackrel{~}{\chi }`$ event rate has then been evaluated for a $`10\mathrm{kg}`$ $`{}_{}{}^{3}\mathrm{He}`$ matrix, to be compared with the background rate . A large number of models are giving a rate higher than the estimated false event rate induced by neutrons ($`10^1\mathrm{day}^1`$), or above the estimated muon background ($`10^2\mathrm{day}^1`$) . The $`\mu `$ background level ($`10^2\mathrm{day}^1`$) is chosen as the lowest reachable limit for MACHe3. Models giving a rate higher than the $`\mu `$ background are selected. Figure 4 shows how they are distributed in the scalar cross section on proton neutralino mass diagram. DAMA region is displayed as well as exclusion curves from Edelweiss and CDMS and their projections. It can be seen that many SUSY models lie below the projected limits of future scalar detectors (Edelweiss , CDMS ), while giving an event rate above the value taken as the lowest reachable limit for MACHe3.

## 4 Conclusions

Detection principle and cosmic muon detection in the elementary component of our matrix has been shown. Background rejection has been presented. It has been highlighted that a $`10\mathrm{kg}`$ high granularity $`{}_{}{}^{3}\mathrm{He}`$ detector (MACHe3) would allow to obtain, in many SUSY models, a $`\stackrel{~}{\chi }`$ event rate higher than the estimated background. MACHe3 would thus potentially allow to reach a large part of the SUSY region, not excluded by current collider limits and projection limit of runing detectors. An experiment on a multicell prototype as seen on figure 5 devoted to validate correlation among the cells for background rejection is in progress.