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# Direct Evidence of the Discontinuous Character of the Kosterlitz-Thouless Jump

## I Introduction

The Kosterlitz-Thouless(KT) transition has attracted a steady interest since its discovery. ber ; kt  This is both because its unusual characteristic properties and its applicability to many systems with two-dimensional (2D) character, like, e.g., superfluid/superconducting films. minnhagen\_rev  The critical properties are given by Kosterlitz’s renormalization equations (KRE).k  A key characteristic feature is the discontinuous universal superfluid jump to zero at the transition. kn  The generic model for the KT transition is the two-dimensional XY model and in this case the discontinuous jump is associated with the helicity modulus. kt ; ber  The 2D XY model has been the subject of very many computer simulations directed at verifying or disproving the various characteristics of the KT transition as given by KRE. ki ; jkk  Although the general consensus is that the 2D XY model does indeed undergo a KT transition, there have also been claims from simulations that the predictions from KRE may not be entirely correct. ki ; jkk  In particular, these earlier works have been focused on the question whether or not the divergence of the correlation length (when the transition is approached from above), is governed by an essential singularity, as predicted by KRE, or by a conventional power-law singularity. Some evidence for the latter possibility was found in Refs. jkk, ; sspl, . Alternatively, in Ref. ki,  it was argued that the divergence is given by an essential singularity which is not entirely consistent with KRE. All this reflects the difficulty of verifying the precise nature of the transition through computer simulations. egs

Similarly, it is difficult to directly verify from simulations that there is a discontinuous jump in the helicity modulus as predicted by KRE. The reason for this is illustrated in Fig. 1: Simulations can only be performed on a finite systems, resulting in the helicity modulus as a continuous function without any singularity. As seen in Fig. 1 the drop at the transition gets steeper and steeper as the system size is increased. However, the size dependence is shown to be rather weak. Consequently, although numerical results like those presented in Fig. 1 for the helicity modulus are consistent with a discontinuous jump for an infinite system size, one cannot on this evidence alone, exclude the possibility that the helicity modulus remains continuous in the thermodynamic limit. The correctness of the discontinuous character of the jump has in practice only been verified from simulations in more indirect ways which make use of additional KRE-predictions for the KT transition like e.g. that the leading size dependence of the helicity modulus at the critical temperature is logarithmic. wm

Thus one may ask if there exists a more direct way of inferring from simulations that there is a discontinuous jump, without resorting to more indirect methods which use additional KRE predictions. In this paper we show that such a more direct way does indeed exist.

Our approach is based on the calculation of a higher order correlation function. This correlation function appears to give an additional and somewhat unexpected characteristic feature of the KT transition. We speculate that this feature might be associated with a universal number akin to the universal value of the helicity modulus at the critical temperature.

## II Model

The 2D XY model on a square lattice of the size $`L\times L`$ is defined by the Hamiltonian

$$H=J\underset{ij}{}\mathrm{cos}\left(\varphi _{ij}\theta _i\theta _j\frac{1}{L}𝐫_{ij}𝚫\right),$$
(1)
where $`J`$ is the coupling strength (set to unity from now on), the sum is over nearest neighbor pairs separated by the displacement $`𝐫_{ij}=\widehat{𝐱}`$ or $`\widehat{𝐲}`$ (we set the lattice spacing $`a1`$), and the phase angle $`\theta _i`$ ($`0\theta _i2\pi `$) at the lattice point $`i`$ satisfies the periodicity $`\theta _{i+L\widehat{𝐱}}=\theta _{i+L\widehat{𝐲}}=\theta _i`$. For generality, we have also included an externally imposed global twist across the sample, $`𝚫=(\mathrm{\Delta }_x,\mathrm{\Delta }_y)`$, defined by that the summation of the phase difference $`\varphi _{ij}`$ along the $`x`$ ($`y`$) direction equals $`\mathrm{\Delta }_x`$ ($`\mathrm{\Delta }_y`$). The partition function $`Z`$ is given by

$$Z=\underset{i}{}\frac{d\theta _i}{2\pi }\mathrm{e}^{H/T}$$
(2)
and the free energy by $`F(𝚫)=T\mathrm{ln}Z`$. The ground state corresponds to the configuration where all spins point in the same direction (i.e., all $`\varphi _{ij}=0`$) which means that the minimum of the free energy corresponds to $`𝚫=0`$. From the symmetry in the Hamiltonian, all odd-order derivatives such as $`F/\mathrm{\Delta }|_{\mathrm{\Delta }=0}`$ and $`^3F/\mathrm{\Delta }^3|_{\mathrm{\Delta }=0}`$ vanish. Accordingly, in the following we will from standard Monte Carlo simulations obtain the two first nonvanishing derivatives of the free energy with respect to $`𝚫`$ at $`𝚫=0`$, i.e., the second order modulus, usually called the helicity modulus, $`\mathrm{{\rm Y}}^2F/\mathrm{\Delta }^2|_{\mathrm{\Delta }=0}`$, and the 4th order modulus $`\mathrm{{\rm Y}}_4^4F/\mathrm{\Delta }^4|_{\mathrm{\Delta }=0}`$, where $`\mathrm{}`$ denotes the thermal average. The former (the helicity modulus) can be expressed as

$$\mathrm{{\rm Y}}=e\frac{L^2}{T}s^2$$

where

$$e\frac{1}{L^2}\underset{ij_x}{}\mathrm{cos}(\theta _i\theta _j),$$

$$s\frac{1}{L^2}\underset{ij_x}{}\mathrm{sin}(\theta _i\theta _j),$$

and the sum is over all links in one direction. This means that $`e`$ is the energy per link and $`s`$ is the average current per link in one direction (here taken to be the $`x`$ direction). Note that $`s=0`$ by symmetry, in contrast to the current-current correlation $`s^2`$ which measures the current fluctuation. The fourth-order modulus can be expressed as

$$L^2\mathrm{{\rm Y}}_4=4\mathrm{{\rm Y}}+3\left[e\frac{L^2}{T}(\mathrm{{\rm Y}}\mathrm{{\rm Y}})^2\right]+\frac{2L^6}{T^3}s^4$$
(3)
In the following, we will measure these two correlation functions, $`\mathrm{{\rm Y}}`$ and $`\mathrm{{\rm Y}}_4`$, in standard MC simulations to demonstrate the existence of a discontinuous jump of the helicity modulus to zero at the phase transition.

## III Stability Argument

Since the global minimum of the free energy $`F(\mathrm{\Delta })`$ corresponds to zero twist, it follows that $`F(0)F(\mathrm{\Delta })`$. To lowest orders in the $`\mathrm{\Delta }`$ expansion we have

$$F(\mathrm{\Delta })=\mathrm{{\rm Y}}\frac{\mathrm{\Delta }^2}{2}+\mathrm{{\rm Y}}_4\frac{\mathrm{\Delta }^4}{4!}$$

This means that $`\mathrm{{\rm Y}}0`$ since the lowest order nonvanishing derivative of the free energy will always dominate for small enough $`\mathrm{\Delta }`$. However, it also implies that the next order derivative $`\mathrm{{\rm Y}}_4`$ likewise has to be $`0`$ at any $`T`$ where $`\mathrm{{\rm Y}}=0`$ in the thermodynamic limit. Our argument is then the simple observation that $`\mathrm{{\rm Y}}`$ cannot go continuously to zero at the transition temperature $`T_c`$ if $`\mathrm{{\rm Y}}_4`$ at the same time approaches a nonzero negative value at $`T_c`$. But, since $`\mathrm{{\rm Y}}`$ is indeed zero in the high-temperature phase, this means that if $`\mathrm{{\rm Y}}_4`$ approaches a negative value at $`T_c`$ then the jump has to be discontinuous. The point is, as we will show below, that the conclusion that $`\mathrm{{\rm Y}}_4`$ is nonzero and negative at $`T_c`$ can be convincingly drawn from standard MC simulations.

## IV Simulation Results

Our simulation of the helicity modulus for 2D XY model is shown in Fig. 1 up to sizes $`L=64`$. The conclusions which can safely be drawn by analyzing the finite size dependence of $`\mathrm{{\rm Y}}`$ is that it is finite in the low temperature phase and is zero in the high temperature phase. Since this is well established we will not discuss it further here. As mentioned in Sec. I, the difficult part from a simulation aspect is to determine how the helicity modulus approaches zero at $`T_c`$ in the thermodynamic limit.

To this end we will use the stability argument given above and instead focus on the size dependence of the correlation function $`L^2\mathrm{{\rm Y}}_4`$ (see Fig. 2). Figure 2(a) shows that $`L^2\mathrm{{\rm Y}}_4`$ vanishes in the high-temperature phase and goes to a nonzero negative value in the low temperature phase as the system size becomes larger. The interesting features is the divergent dip. This occurs in the region where the helicity modulus for finite $`L`$ goes rapidly towards zero. Thus this singularity in $`L^2\mathrm{{\rm Y}}_4`$ can safely be associated with $`T_c`$. The conclusion from Fig. 2(a) is that $`L^2\mathrm{{\rm Y}}_4`$ diverges at $`T_c`$ for $`L\mathrm{}`$, goes to zero above, and goes to a negative nonzero value below. This conclusion is further supported by the fact that the half-width of the divergent dip decreases towards zero for $`L\mathrm{}`$ as illustrated in the inset of Fig. 2(a). The crucial point is now what this divergence in the correlation function $`L^2\mathrm{{\rm Y}}_4`$ implies for $`\mathrm{{\rm Y}}_4`$. This is shown in Fig. 2(b), which gives the result for $`L12`$. The inset in Fig. 2(b) gives the depth of the dip as a function of size. As is apparent from the inset, the depth goes to a finite value in the thermodynamic limit. Linear extrapolation in $`1/L`$ to $`L=\mathrm{}`$ gives the value $`0.130\pm 0.005`$. Thus we conclude that $`\mathrm{{\rm Y}}_4`$ is indeed negative and nonzero precisely at $`T_c`$. Using the stability argument in Sec. III this means that the helicity modulus has to be positive and nonzero precisely at $`T_c`$. However, above $`T_c`$ the helicity modulus is zero from which follows that the helicity modulus has to be discontinuous at $`T_c`$.

One may also note from Fig. 2(b) that the position of the minimum of the dip decreases towards lower $`T`$ with increasing $`L`$. However, the approach towards the known value of $`T_c`$ ($`0.89`$) is rather slow making a precise determination of $`T_c`$ based on $`\mathrm{{\rm Y}}_4`$-data less advantageous.

## V Final Remarks

We have shown that the discontinuous character of the jump of the helicity modulus at the transition for the 2D XY model can be established from MC simulations of the 4th order modulus given by Eq.(3). It seems very likely that the singularity found here for the 4th order modulus in case of the 2D XY model is part of the general KT transition scenario. Thus we suggest that it sometimes may be advantageous to study the singularity of this 4th order modulus in simulations, when trying to determine if a transition for a particular model is of KT type. It is also tempting to speculate that the finite value of $`\mathrm{{\rm Y}}_40.130`$ at $`T_c`$ is associated with a universal number, akin to the universal value of of the helicity modulus $`\mathrm{{\rm Y}}=2T_c/\pi `$.

## Acknowledgements

Support from the Swedish Natural Research Council through Contract No. F 5102-659/2001 is gratefully acknowledged. B.J.K. was supported by the Korea Science and Engineering Foundation through Grant No. R14-2002-062-01000-0.


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# First-principles study of adhesion at Cu/SiO2 interfaces

## I  Introduction

Adhesion of thin metal films to glass substrates have continued to be the subject of intense study for many years because of its importance to the large-area electronics industry. Copper in particular, a noble metal with a high bulk thermal and electrical conductivities, and apparently low electromigration rate, is an excellent candidate for interconnects in integrated circuitry on dielectric substrates, and thus the formation of a strong and highly reliable interface between copper and glass has been an issue of primary importance. Unfortunately, Cu films are often reported to bind rather poorly to oxide-based glass substrates, and films that do adhere at room temperature can show diminished adhesivity after thermal cycling, an effect often attributed to differences of thermal expansion between Cu and the oxide substrate. In many studies, poor bonding is frequently explained by noting that since Cu does not reduce SiO2, a graded oxide layer facilitating the adhesion is unable to form. Chemically, copper possesses a half-empty $`s`$ shell and a reasonably tightly-bound and filled $`d`$-shell, and thus is less reactive than aluminum and many transition metal films, which oxidize well and are observed to adhere more reliably. Thus it is not surprising that adhesion is often improved experimentally by applying transition metal intermediary layers prior to Cu film deposition, or alloying the Cu films with small amounts of Mg or Al.

Adhesion of copper films to oxide glasses is, of course, expected to be highly sensitive to the temperature, oxygen partial pressure, and the condition of the glass surface prior to deposition. A common feature of many studies of Cu films on glass is that they were performed under conditions amenable to surface passivation either before or during deposition of the copper film. For example, Cu films sputtered under high purity conditions in a vacuum do adhere to glass substrates. In particular, Ohmi et al. demonstrated robust adhesion of copper to glass after removing hydroxyl (OH) groups from the interface in situ just prior to deposition. This suggests that dangling bonds at moisture-free glass surfaces would be readily saturated by Cu-O bonds.

Glasses important to industry can be chemically complex, often containing a substantial amount (perhaps $`30`$%) of aluminum, boron, and other alkaline earth elements. Their primary component, however, is almost always SiO2, which by itself forms one of the simplest glasses, amorphous silica (a-SiO2). In the interest of simplifying the chemistry, we shall restrict our focus to chemically-pure SiO2 glasses for the duration of this study. Amorphous silica has no long range order yet remarkably, on length scales comparable to a Si-O bond, it is nearly perfectly ordered: the bond-length does not vary appreciably from 1.61 Å; each Si atom is tetrahedrally coordinated with O atoms, and the bonds are primarily of a covalent nature. At length scales between 5 Å and 8 Å, minimal variations in O-Si-O and Si-O-Si bond angles result in an appreciable degree of intermediate range orientational disorder. Previous work using molecular dynamics has been performed on both bulk vitreous silica and silica surfaces. Much of it was based on semi-empirical potentials, which though able to simulate systems large enough to correctly capture the effects of the intermediate range orientational disorder, are expected to be far less accurate when local conditions deviate from those in the bulk, such as they do at surfaces or interfaces.

Since microscopically adhesion is related to the strength of the electronic bond between atoms at the interface, the local electronic structure at the interface will play an important role in understanding the reactivity of the metal with the oxide substrate. A first principles treatment would therefore be most appropriate for examining the nature of local bonding at an ideal interface between the two systems, and indeed this approach has proved insightful in the past for studying adhesion between metal films and insulating substrates. Previous first-principles work on the $`\alpha `$quartz surface observed significant changes in bonding near the surface; to our knowledge, however, the effects of metallic overlayers on SiO2 surface geometries and electronic properties have yet to be examined from first principles.

In this article, we assess the degree to which the chemical bonding at atomically-sharp interfaces reflects the empirical trends in the adhesion of metallic contacts to glass substrates through study of a simplified system, Cu monolayers on $`\alpha `$cristobalite, a crystalline SiO2 polymorph which although ordered does possess a density quite close to that of a-SiO2. Adhesion is studied as a function of oxygen surface coverage from first principles, using density functional theory within the local density approximation (LDA). Our methods allow us to elucidate the role of local chemistry in binding the film to glass, but require us to neglect its inherent long-range disorder and also, to a limited extent, its intermediate-range orientational disorder. Since we are chiefly interested in the local bonding properties, which are expected to be the same for both amorphous and crystalline silica, the loss of disorder is acceptable. We summarize the method and approximations used here in Sec. II; in Sec. III we describe the relaxed 1$`\times `$1 $`\alpha `$-cristobalite(001) surfaces considered here, which include both stoichiometric and non-stoichiometric surface terminations, chosen so as to reflect different possible oxygen coverages that may result from different deposition conditions. In Sec. IV, we detail results of atomic relaxation of Cu/SiO2 interfaces, where the adhesion is found to be critically sensitive to oxygen density at the substrate surface, and where relatively strong bonding is reported for oxygen-rich surfaces. The effect of hydroxyl groups as a surface passivator is also briefly considered by calculating adhesion energies between copper monolayers and a hydroxyl-terminated SiO2 surface. After discussing our results and their implications, we provide concluding remarks in Sec. V.

## II  Methodology

### A Computational details

Our first-principles density-functional calculations are carried out within the LDA, using the correlation energy of Ceperley and Alder, as implemented within the Vienna ab initio Simulation Program (VASP). We use a plane-wave basis set with a 29 Ry cut-off, and ultrasoft pseudopotentials for Cu and H, projector augmented-wave potentials for O, and a norm-conserving pseudopotential for Si. The Monkhorst-Pack $`𝒌`$point mesh is chosen so that $`n_k=3\times 3\times 1`$ for the $`5\mathrm{\AA }\times 5\mathrm{\AA }\times 30\mathrm{\AA }`$ supercell which is used in this work. Also, we make use of a Fermi-distribution smearing with the temperature of $`k_BT0.2`$ eV to facilitate rapid convergence. These computational conditions provide good convergence of the structure, density of states, and energy differences given here, and are used throughout this work unless otherwise stated.

It should be mentioned that the $`𝒌`$point sampling discussed above is not entirely sufficient for study of the bulk properties of copper. In fact, the total energy of bulk copper obtained with this sampling is converged to about 0.02 eV per Cu atom. However, a sparser mesh turns out to be adequate for this study since energy differences are converged. To demonstrate, we increased our sampling to $`n_k=4\times 4\times 1`$ for the supercell mentioned above, recalculated total energies and forces, and found that the resulting difference in adhesion energy is less than 4% even in the largest case.

### B Bulk properties of constituent systems

Copper crystallizes in the fcc structure under normal conditions and its lattice constant is 3.615 Å at 291 K. The LDA underestimates this lattice constant as is well known, and we obtain 3.532 Å for the equilibrium value as shown in Table I, in agreement with a previous LDA study. At equilibrium we find $`a`$ = 4.975 Å and $`c`$ = 6.907 Å for the tetragonal cell of bulk $`\alpha `$-cristobalite (the $`P4_12_12`$ structure), in excellent agreement with experiment and previous LDA calculations. Further, the computed Si-O bond length ($`1.606`$ Å) is remarkably close to experiment ($`1.603`$ Å), and the calculated O-Si-O bond angle is near the tetrahedral ideal value, also in-line with measurement. Conveniently, the choice of $`\alpha `$-cristobalite circumvents spurious lattice mismatch when considering the interfaces with Cu overlayers: Compare the lattice constant $`a`$ of $`\alpha `$cristobalite with $`\sqrt{2}a`$ of Cu in Table I.

## III  (001) surfaces of $`\alpha `$cristobalite S$`𝐢`$O2

As a starting point, we consider an $`\alpha `$cristobalite slab consisting of 5 SiO2 layers, the thickness of which is $``$8.3 Å. Translational symmetry is removed along the $`c`$-axis, defining two different (001) surfaces perpendicular to this axis. We embed this $`\alpha `$-cristobalite slab, along with about 20 Å of vacuum, within a supercell having dimensions of 5 Å$`\times `$5 Å$`\times `$30 Å. Oxygen number at the top of our SiO2 slab is then changed to mimic different substrate terminations. Two nonbridging oxygen atoms terminate the bottom of the slab, and two additional H atoms are attached to the oxygens to remove dangling bonds. Forces on the atoms are computed using the Hellmann-Feynman theorem, and the positions of atoms are then updated until the total energy reaches a minimum. The oxygen atoms at the bottom surface, terminated by hydrogens, are fixed at their bulk positions in order to reduce size effects owing to the finite thickness of the SiO2 slab, though the positions of each of the hydrogen atoms are permitted to relax. Previous first-principles calculations of $`\alpha `$-quartz surfaces and model Si/SiO2 interfaces have indicated that about 5 Å away from the interface, the local structural and electronic properties of the slab are bulk-like, and thus the size of our slab is sufficient to approximate both surface and bulk features.

Figure 1 presents views of the relaxed $`\alpha `$-cristobalite(001) surfaces. Supercells with slabs having three different surface terminations are considered in this work, which we label as Si-, O-, and OO-terminated. The Si-terminated slab contains five SiO2 units together with two bottom hydrogens; the O-terminated slab is identical to the Si-terminated except that the dangling surface oxygen atom is added; the OO-terminated slab is again a modification of the Si-terminated slab in which two oxygens are added to the surface. Bond lengths and angles are not expected to remain bulk-like at the surface, where the choice of termination can leave non-bridging oxygens with dangling bonds at the surface (e.g., in the OO-terminated cases). Indeed, we find that relaxation significantly changes the Si-O bond lengths within two atomic layers from the surface for all terminations considered, and the nature of these changes is strongly dependent on the termination. In the Si-terminated case, the additional charge carried by the dangling Si bonds forces the Si surface atom above the plane of the surface; as a result the Si-O bonds supporting it from below elongate slightly to 1.64 Å. In the O-terminated case, the surface O atom, bonded to only one other Si, relaxes downward into the surface, and its bond length decreases by more than 5% from 1.6 Å to 1.5 Å. In the OO-terminated case, in some contrast to the Si- and O-terminated slabs, the Si-O bond lengths remain essentially the same as bulk. But the distance between O neighbors on the surface is also 1.6 Å, which is very small compared with typical bulk O second neighbor distances of 2.7 Å. Thus O atoms may evidently saturate dangling bonds through bonding with neighboring O atoms at this surface.

As expected, the total cohesive energies of the supercells decrease substantially with each additional O atom: adding one oxygen atom or two oxygen atoms lowers the cohesive energy by $``$7.1 eV or $``$11.3 eV per surface Si, respectively. Since the energy required to break the O2 bond is nearly 5 eV per molecule, this energy comparison suggests that the OO-terminated surface may be the most stable of the three terminations, and the O-terminated surface the second. Evidently our first-principles calculations are consistent with the intuition that glass surfaces should be oxygen-rich.

## IV  C$`𝐮`$/S$`𝐢`$O2 interfaces: results and discussion

### A  Interfacial structure

We now add five Cu layers to each of the fully-relaxed (001) $`\alpha `$-cristobalite surfaces, obtained as discussed above in Sec. III. The Cu layers are initially positioned on the surface so that a Cu atom in the lowest monolayer lies on the former symmetry axis of the $`\alpha `$-cristobalite slab. The length of the supercell lattice vector normal to the surface (the $`c`$-axis) is fixed to 30 Å as in Sec. III, a value we find to be large enough to accommodate up to five additional Cu layers while keeping the interactions between the surfaces in neighboring supercells minimal. Each monolayer in our supercell contains four Cu atoms, and before relaxation each Cu atom has four intralayer neighbors at a distance of 2.5 Å. Fortunately, the lattice parameter of the $`1\times 1`$ surface of $`\alpha `$-cristobalite is well matched to that of the $`\sqrt{2}\times \sqrt{2}`$ surface of copper as shown in Table I (the mismatch is less than 1%). The small lattice mismatch is artifact of our approximate treatment of amorphous silica as crystalline. In reality, stress induced by lattice-matching is relieved through formation of defects and/or dislocations. (In the case of a truly amorphous substrate, stress may also be overcome through surface reconstruction, a complexity we neglect in the present work.)

The positions of all atoms in the supercell are again relaxed except for the bottom O atoms, and Fig. 2 shows the optimized structures of the interfaces for each termination. The most significant reconstruction at the interface is observed in the OO-terminated case. The O-O bond observed at the free $`\alpha `$-cristobalite surface in Fig. 1 is broken by the deposition of copper, and the O-Si-O angle is changed from 59 to 104 with the Si-O bond lengths kept almost constant. This large rearrangement would indicate bond formation between interfacial O and Cu atoms, suggesting good chemical adhesion between the oxide substrate and the Cu film. Each interfacial O atom has two Cu neighbors, and the Cu-O bond lengths are computed to be $`1.9`$ Å, strikingly similar to Cu-O distances found in cuprates, where each copper atom is coordinated by four oxygens and considered to be in a Cu2+ state. Similar Si-O and Cu-O bond lengths are observed at the interface between O-terminated surfaces and Cu monolayers, although the Si-O-Cu angles are smaller than in the OO-terminated case by $`15^{}`$, as can be seen in Fig. 2. The magnitude of the reconstruction at the O-terminated/Cu interface is less than that at the OO-terminated/Cu interface.

The interface between the Si-terminated substrate and Cu is completely different from either of the oxygen terminated interfaces. In this case, the interfacial Si atom possesses four Cu neighbors, each with bond length $`2.4`$ Å, and there is negligible atomic rearrangement, implying more metallic-like bonding.

### B Electronic properties

To investigate further the bonding properties of each interface discussed above, we compute the site-projected local density of states (LDOS) for atoms near the interfaces, and compare them with those obtained for bulk-like atoms deeper inside the slabs; the LDOS are shown together for each interface in Fig. 3. In the OO-terminated case, significant hybridization is observed between Cu$`d`$ and O$`p`$ states just below the Fermi level. A key feature is the slight bump in the O$`p`$ LDOS, lying about 1 eV below the Fermi energy, which becomes progressively smaller with decreasing O content at the interface, and nearly vanishes in the Si-terminated case. Evidently strong hybridization between Cu$`d`$ and O$`p`$ states is responsible for the significant reconstruction at the OO-interface. It is worth pointing out here that as the number of O atoms at the interface is decreased, the Si$`sp`$ LDOS around the Fermi energy increases, that is the interfacial bonding takes on a more metallic character. This behavior results from the hybridization of Si$`sp`$ states with the itinerant Cu$`s`$ states around the Fermi energy. In addition, we observe the bandgap computed within the LDA (an underestimate of the true bandgap) opens and gradually approaches its bulk LDA value for LDOS in the middle of the SiO2 slab, confirmation that our slab exhibits approximate bulk behavior away from the interface.

To examine the degree to which changes in structural and bonding properties are confined to the interface, and to observe the mixing between the electronic states of the SiO2 substrate and the Cu layers in more detail, we calculate the density difference from the superposition, namely,

$`\delta n(z)`$ $`=`$ $`n_{\mathrm{IF}}(z)\left[n_{\mathrm{SiO}_2}(z)+n_{\mathrm{Cu}}(z)\right],`$ (1)
where $`n_{\mathrm{IF}}(z)`$, $`n_{\mathrm{SiO}_2}(z)`$, and $`n_{\mathrm{Cu}}(z)`$ are the densities of the Cu/SiO2 interface, the SiO2 substrate, and the Cu layers, respectively, averaged over the $`xy`$ plane (parallel to the interface). To obtain $`n_{\mathrm{SiO}_2}(z)`$ ($`n_{\mathrm{Cu}}(z)`$), we simply remove the Cu layers (SiO2 substrate) from the fully relaxed interface in the supercell, and then recalculate the electronic structure self-consistently keeping the atoms fixed. The quantity $`\delta n(z)`$ thus indicates the change in electron density resulting from chemical bonding between the Cu layers and the SiO2 substrate. (To simplify the analysis, we are neglecting additional changes stemming from the atomic rearrangements at the free surfaces of SiO2 and Cu.) The results of calculations of the $`\delta n(z)`$ appear in Fig. 4. The $`\delta n(z)`$ in the OO-terminated case most prominently deviates from zero around the interface, reflecting significant charge transfer between the two slabs. The charge transfer in the O- and Si-terminated cases is comparatively much smaller. In particular, in the Si-terminated case, the depletion of the density in the vicinity of the lowest Cu layer is not so drastic, suggesting that the localized Cu$`d`$ states have less influence on the bonding around the interface.

### C Quantitative analysis of adhesion

To assess the adhesive strength of the interfaces, we have calculated the ideal work of separation, or adhesion energy, per unit area $`W`$ from

$`W`$ $``$ $`(E_{\mathrm{SiO}_2}+E_{\mathrm{Cu}}E_{\mathrm{IF}})/A,`$ (2)
where $`E_{\mathrm{SiO}_2}`$, $`E_{\mathrm{Cu}}`$, and $`E_{\mathrm{IF}}`$ are the energies of the isolated SiO2 substrate, Cu layers, and Cu/SiO2 interface in the supercell, respectively, and $`A`$ is the area. Physically, the adhesion energy $`W`$ is the work per unit area required to separate the interface into the Cu layers and the SiO2 substrate within a microcanonical process, and it can be considered a measure of the strength of the adhesion. For the purposes of comparison, all energies are calculated using supercells of the same size (5 Å$`\times `$5 Å$`\times `$30 Å) independent of whether it contains Cu layers, any of the SiO2 substrates, or Cu/SiO2 interfaces. Table II lists the adhesion energy for each case. The adhesion energy in the OO-terminated case turns out to be much larger than those in the O- and Si-terminated cases, and comparable to values previously computed for other metal-dielectric interfaces, such as Co/TiC (Ref. ) and Nb/Al2O3 (Ref. ). We note that the computed energies for the OO-terminated case, $``$ 4 J/m2, are consistent with values obtained experimentally by Kriese et al. for 100 nm thick films of Cu on SiO2 using an indentation technique. In summary, the magnitudes of adhesion energies computed here for each of the three different interfaces reflect the trends witnessed above in their structural and bonding properties.

#### 1 Local atomic structure

At this point, it is meaningful to investigate further a drawback of using crystalline $`\alpha `$cristobalite to model the amorphous substrate. When Cu layers are placed on an amorphous SiO2 substrate, different local atomic configurations are possible at the interfaces because of the non-periodicity of glass. A principal simplification of our model is the imposition of translational symmetry: we are unable to directly assess the difference between the adhesive properties of crystalline substrates and those of amorphous substrates. We are, however, able to investigate the sensitivity of our calculated adhesion energies to changes in local atomic structure. As a first step, we compute the influence of the position of Cu layers, relative to the substrate, on the adhesion energy by translating the Cu layers in the $`xy`$ plane.

As shown in Fig 5, the adhesion energy turns out rather insensitive to the initial position of the Cu layers so long as the termination type remains unchanged. This result suggests that the adhesive properties realized in these $`\alpha `$cristobalite substrates may well be carried over, to some extent, to those of glass substrates. The insensitivity of adhesion energy to the position of Cu layers does not imply that the detailed structure at the interface is less important for adhesion. In fact, as shown in Fig. 6 for the OO-terminated case, atoms at the interfaces do move significantly relative to the unshifted case. Since the surface atoms have a greater freedom to choose their position than those in bulk, the adhesion energy remains rather constant for various initial positions of Cu layers.

#### 2 Local oxygen surface coverage

Thus far we have investigated the Si-, O-, and OO-terminations independently. Depending on the oxygen partial pressure, however, these terminations are generally expected to coexist on the substrate surface, independent of whether the substrate is crystalline or amorphous. To examine the effects of oxygen surface densities intermediate between those of the Si-, O-, and OO-terminated cases, we enlarge the supercell by a factor of two along the $`y`$-axis (along the horizontal direction of Figs. 1, 2, and 6). For the 1$`\times `$2-supercells, three new surfaces, in addition to those already considered above, are now possible. These are: a (Si,O)-terminated surface which consists of neighboring Si- and O-terminated surfaces; a (Si,OO)-terminated surface which consists of neighboring Si- and OO-terminated surfaces; and a (O,OO)-terminated surface which consists of neighboring O- and OO-terminated surfaces. \[Note that the (Si,OO)-terminated case possesses the same oxygen density as the O-terminated case.\] We find that the (Si,OO)-terminated substrate has energy which is higher than that of the O-terminated surface by $`1.4`$ eV per Si atom at the surface (per 25 Å2). Therefore, we restrict our focus to investigation of the (Si,O)- and (O,OO)-terminated cases, calculating their relaxed structures and adhesion energies.

Figure 7 depicts the adhesion energy as a function of the oxygen density at the interface. Remarkably, the adhesion energy is not a monotonically-increasing function of oxygen density; at low oxygen density, increasing the number of O atoms a small amount does not necessarily lead to stronger adhesion. However, beyond the oxygen density of 4 nm-2 where the OO-termination will begin to appear appreciably, the adhesion energy increases, and does so almost linearly. This linear dependence implies that each OO surface unit contributes to the adhesion fairly independently, and thus the locally OO-terminated regions may not necessarily have to form large domains in order to work as an effective “glue”, although it is clear that a critical density of such locally OO-terminated regions is required for strong adhesion.

#### 3 Hydroxylated surfaces

We now address a frequently-cited reason for the weak adhesion at Cu/a-SiO2 interfaces, namely the existence of hydroxyl groups on the SiO2 surface. It is well known that hydroxyls are likely to form on the SiO2 surface under “wet” deposition conditions; to examine the impact of hydroxyls on adhesion from first-principles, we add two hydrogens to the 1$`\times `$1 OO-terminated surface, and relax all of the atoms. The result is that the cohesive energy of OHOH-terminated substrate, in which a Si atom is terminated by two hydroxyls, is lower than that of OO-terminated substrate by $``$ 11.2 eV per surface Si atom. This energy difference is much larger than the dissociation energy of H2 molecule ($`4.5`$ eV per molecule), suggesting the high stability of the OHOH-terminated substrate. If we now place the Cu layers on top of the hydroxylated surface and relax the interface (Fig. 8), we find that the deposition of Cu layers does not significantly affect the structure at the OHOH-terminated surface, implying little interaction; the hydrogen present at the surface leaves the surface neutral and inert. This tendency is clearly reflected in the calculated adhesion energy, and according to our calculations it is just 0.331 J/m2, less than one tenth of the adhesion energy observed in the OO-terminated case.

However, as shown in Table II, the adhesion energies for all other cases studied here (i.e. the OO-, O-, and Si-terminated cases) seem to be of a magnitude which should produce adhesion, especially the oxygen-rich OO-terminated case. It is also noteworthy that the OO-terminated substrate, which has the largest adhesion energy among the three, looks actually the most stable substrate. These facts imply that should dehydroxylation of the substrate surfaces be successfully achieved (e.g. by annealing or particle bombardment of a growing film surface), robust adhesion is entirely possible, at least from the point of view of chemical bonding.

## V  Conclusions

We have performed a first-principles study of the adhesive properties of atomically-sharp Cu/SiO2 interfaces. As a model a-SiO2 substrate, we used a crystalline polymorph of SiO2, $`\alpha `$cristobalite, and investigated its Si-, O-, and OO-terminated (001) surfaces in detail. For interfaces between Cu and OO-terminated surfaces, a substantial rearrangement of oxygen positions relative to the free surface is observed, suggesting the formation of strong Cu-O bonds. Analysis of the local density of states at the interface showed that Cu-O interfacial bonds are composed of Cu$`d`$ and O$`p`$ states. The computed adhesion energy also exhibited a tendency toward much stronger adhesion in the OO-terminated interface than in the O- and Si-terminated interfaces: Substrate surfaces with high oxygen content were found suitable for adhesion.

The adhesion energy is found to be very insensitive to the position of the Cu layers if the termination type is unchanged, and this observation suggests that $`\alpha `$cristobalite may serve as a good starting model of a-SiO2 substrates. The detailed dependence of the adhesion energy on oxygen density at the substrate surface has been investigated, and it shows that the surfaces where the O- and OO-terminations coexist can also lead to relatively strong adhesion.

The possible existence of hydroxyl groups at the substrate surface is thought to be the main cause for the weak adhesion observed in experiment. However, if these hydroxyls are removed beforehand and the oxygen density at the surface is increased (for example, by upping the oxygen partial pressure), Cu layers are predicted to adhere reasonably well to SiO2. In addition to the possibility of direct comparison to future measurements on crystalline Cu/$`\alpha `$-cristobalite(001) interfaces, these results should serve as a starting point for which to study more complicated interfacial geometries, benchmarks for future investigations, and a baseline for experiments attempting to elucidate complicated phenomena affecting adhesion at Cu/glass interfaces.

## VI Acknowledgments

We thank S. Baker and M. Backhaus for helpful discussions. This work was supported by the National Science Foundation (DMR-9988576), and made use of the Cornell Center for Materials Research Shared Experimental Facilities, supported through the National Science Foundation Materials Research Science and Engineering Centers program (DMR-9632275).


text:
# Modularity of rigid Calabi-Yau threefolds over ℚ

## 1 Introduction

Let $`X`$ be a rigid Calabi-Yau threefold defined over $`.`$ Recall that (see , ) $`X`$ is a smooth projective threefold over $`,`$ and satisfies

1. $`H^1(X,𝒪_X)=H^2(X,𝒪_X)=0,`$
2. $`^3\mathrm{\Omega }_X^1𝒪_X,`$ and
3. $`h^{2,1}(X)=0.`$

The first two of these conditions define a Calabi-Yau threefold, while the third signifies rigidity. In a certain sense, rigid Calabi-Yau varieties are the natural generalization of elliptic curves to higher dimensions.

We approach the issue of modularity for rigid Calabi-Yau threefolds by using Galois representations. For other formulations, see , . Here is how it works: Given a prime $`\mathrm{},`$ the action of $`G_{}`$ on the dual of the étale cohomology group $`H_{\text{ét}}^3(X_\overline{},_{\mathrm{}})`$ defines a continuous, odd, two dimensional representation

$$\rho _{X,\mathrm{}}:G_{}GL_2(_{\mathrm{}}).$$

The representation $`\rho _{X,\mathrm{}}`$ is unramified at a prime not equal to $`\mathrm{}`$ if $`X`$ has good reduction there; its determinant is equal to $`ϵ_{\mathrm{}}^3`$ (where $`ϵ_{\mathrm{}}`$ is the $`\mathrm{}`$-adic cyclotomic character). If $`X`$ has good reduction at $`\mathrm{}`$ and $`\mathrm{}>3`$, it follows from the comparison theorem of Fontaine-Messing (cf. ) that the representation $`\rho _{X,\mathrm{}}`$ is crystalline (locally at $`\mathrm{}`$). Moreover, from the definition of rigid Calabi-Yau it also follows that this local $`\mathrm{}`$-adic representation has Hodge-Tate weights $`\{0,3\}`$.

If $`X`$ has good reduction at $`p`$, we set

$$t_3(p)=\text{tr}\rho _{X,\mathrm{}}(\text{Frob}_p),\mathrm{}p.$$

Of course, the definition is independent of which $`\mathrm{}`$ we choose for calculating the trace. Moreover, the quantity $`t_3(p)`$ is relatively easy to calculate: one only needs to ‘count points’ on the mod $`p`$ reduction of $`X`$ (see Remark 2.9 of  for details).

The Riemann hypothesis, proved by Deligne as part of the Weil conjectures, states that the roots of the characteristic polynomial of $`\rho _{X,\mathrm{}}(\text{Frob}_p)`$, $`p\mathrm{}`$ a prime of good reduction, both have the same complex absolute value. If $`\rho _{X,\mathrm{}}`$ was reducible, its constituents should be $`\mathrm{}`$-adic characters of $`G_{}`$, and so we must have

$$\rho _{X,\mathrm{}}\left(\begin{array}{cc}\mu ϵ_{\mathrm{}}^a& \\ 0& \mu ^1ϵ_{\mathrm{}}^b\end{array}\right)$$

where $`\mu `$ is a finite order character and $`a,b`$ with $`a+b=3.`$ Since this clearly contradicts the Riemann hypothesis as $`ab,`$ we can therefore conclude that $`\rho _{X,\mathrm{}}`$ is irreducible.

###### Conjecture 1.1

Let $`X`$ be a rigid Calabi-Yau threefold over $`.`$ There is then a weight $`4`$ newform $`f`$ on $`\mathrm{\Gamma }_0(N)`$ such that

$$\rho _{X,\mathrm{}}\rho _{f,\mathrm{}}$$

for some (and hence every) prime $`\mathrm{}.`$

We haven’t specified what the level should be in the statement of the conjecture, but it is clear that $`N`$ should only be divisible by primes where $`X`$ has bad reduction. Specifying the level at primes of bad reduction is more problematic: in fact, results of de Jong (see in particular Deligne’s corollary in , Prop. 6.3.2) imply that when $`\mathrm{}`$ ranges through all primes of good reduction of $`X`$, there exists a bound for the (prime to $`\mathrm{}`$ part of the) conductor of $`\rho _{X,\mathrm{}}`$, and this minimal upper bound will turn out to be the level of the associated modular form. However, this value is not effectively computable. As for evidence in support of the conjecture, it is known to be true for all rigid Calabi-Yau threefolds that we know of. (However, we must add that ‘what we know’ contains only a handful of examples!) In the form stated above, the conjecture forms a part of (or rather follows from) the Fontaine-Mazur conjecture on modularity of Galois representations.

In this article, we prove the modularity conjecture for all rigid Calabi-Yau threefolds verifying some local conditions. More precisely, we shall prove the following:

###### Theorem 1.2

Let $`X`$ be a rigid Calabi-Yau threefold over $`.`$ Suppose $`X`$ satisfies one of the following two conditions:

1. $`X`$ has good reduction at $`3`$ and $`7`$; or,
2. $`X`$ has good reduction at $`5`$ and some prime $`p\pm 2(mod5)`$ with $`t_3(p)`$ not divisible by $`5.`$

Then $`X`$ is modular.

###### Remark 1.3

This result applies to all but one (class) of the known examples of rigid Calabi-Yau threefolds.

Acknowledgements: We would like to thank Frazer Jarvis and the referee for various helpful suggestions.

## 2 Modularity of $`\mathrm{}`$-adic representations

More generally, let us consider irreducible continuous representations

$$\rho :G_{}GL_2(_{\mathrm{}}^{ac})$$

which are odd and unramified outside finitely many primes. We also assume that $`\mathrm{}5`$, and that the determinant of $`\rho `$ is $`ϵ_{\mathrm{}}^3.`$ By choosing a stable lattice, we can reduce $`\rho `$ modulo $`\mathrm{}`$ and obtain a unique semi-simple continuous representation

$$\overline{\rho }:G_{}GL_2(𝔽_{\mathrm{}}^{ac}).$$

Following Wiles, one then deduces the modularity of $`\rho `$ from that of $`\overline{\rho }.`$

### 2.1

We shall now describe some results under which such a deduction is possible. We fix $`\rho `$ and $`\overline{\rho }`$ as above (in the beginning of the main section). Throughout this subsection, we shall also suppose that

###### Assumption 2.1

$`\rho `$ is crystalline at $`\mathrm{}`$ with Hodge-Tate weights $`\{0,3\}`$.

The first result we describe is due to Skinner and Wiles (Theorem A, Section 4.5 in ).

###### Theorem 2.2

If $`\overline{\rho }`$ is reducible, then $`\rho `$ is modular.

The only point to be noted is that if $`\overline{\rho }`$ is reducible, then $`\rho `$ is necessarily ordinary at $`\mathrm{}`$, and so the quoted result applies. This follows immediately from Proposition 9.1.2 of , which shows that if $`\rho |_D_{\mathrm{}}`$ is irreducible and crystalline then its reduction is irreducible. (See also  for a similar argument in the case $`\mathrm{}=3`$ , $`w=1`$ where $`w`$ is the non-zero Hodge-Tate weight.)

###### Theorem 2.3

Suppose that $`\rho `$ is ordinary at $`\mathrm{}`$, and also suppose that $`\overline{\rho }`$ is irreducible and modular. Then $`\rho `$ is modular.

This follows immediately from Theorem 5.2 of Skinner and Wiles in : since $`\rho `$ is ordinary at $`\mathrm{}`$ and has determinant $`ϵ_{\mathrm{}}^3`$, we have

$$\overline{\rho }|_I_{\mathrm{}}\left(\begin{array}{cc}ϵ_{\mathrm{}}^3(mod\mathrm{})& \\ 0& 1\end{array}\right)$$

where $`I_{\mathrm{}}`$ is the inertia group at $`\mathrm{}.`$ In particular, it is $`D_{\mathrm{}}`$-distinguished (i.e., the two diagonal characters in the residual representation are distinct). As we have started out with the condition that $`\overline{\rho }`$ is modular, the conclusion above is the one given by Theorem 5.2 of .

The above two results deal with the case when the representation $`\rho `$ is ordinary at $`\mathrm{}.`$ For the case when $`\rho `$ is crystalline but not ordinary, we have the following result of Taylor, :

###### Theorem 2.4

Suppose that $`\rho `$ is not ordinary at $`\mathrm{}`$. Let $`F`$ be a totally real field of even degree such that $`\text{Gal}(F/)`$ is solvable, and such that $`\mathrm{}`$ splits completely in $`F.`$ Assume the following:

* There is a Hilbert modular form of weight 4 and level 1 on $`GL_2(𝔸_F)`$ which gives $`\overline{\rho }`$.
* $`\overline{\rho }`$ restricted to the absolute Galois group of $`F\left(\sqrt{(1)^{(\mathrm{}1)/2}\mathrm{}}\right)`$ is irreducible.

Then $`\rho `$ is modular.

Proof. Using Theorem 2.6 and Theorem 3.2 of , we see that $`\rho |_{G_F}`$ is ‘modular’. Solvable base change results of Langlands then enable us to deduce the modularity of $`\rho `$ from that of $`\rho |_{G_F}`$.  $`\mathrm{}`$

As for the auxiliary totally real $`F`$ that appears in the above theorem, we have the following ‘level lowering’ result of Skinner and Wiles, .

###### Theorem 2.5

If $`\overline{\rho }`$ is irreducible and modular, then we can find a totally real solvable extension $`F`$, and a Hilbert modular form of weight 4, level 1 on $`GL_2(𝔸_F)`$ which gives $`\overline{\rho }`$. (Note that $`\overline{\rho }`$ is ‘crystalline’.) Moreover, given a finite set of primes $`\mathrm{\Sigma }`$ where $`\overline{\rho }`$ is unramified, we can insist that the primes in $`\mathrm{\Sigma }\{\mathrm{}\}`$ split completely in $`F.`$

Proof. This is essentially proved in  (they give a complete proof for the case when the weight is 2).

Firstly, note that (cf. ) we can find a weight 4 newform $`f`$ on $`\mathrm{\Gamma }_0(N)`$ with $`N`$ prime to $`\mathrm{}`$ and divisible only by primes where $`\overline{\rho }`$ is ramified such that

$$\overline{\rho }\rho _{f,\mathrm{}}(mod\mathrm{}).$$

We can therefore find an even degree, totally real, solvable extension $`F_1/`$ in which all the primes in $`\mathrm{\Sigma }\{\mathrm{}\}`$ split completely, and a Hilbert modular form $`f_1`$ over $`F_1`$ of level $`𝔫`$, weight 4, such that

* $`\overline{\rho }_{f_1,\mathrm{}}\overline{\rho }|_{G_{F_1}},`$
* $`𝔫`$ is an ideal dividing $`N`$ (and so is prime to $`\mathrm{}`$), and
* $`\overline{\rho }|_{G_{F_1}}`$ is unramified at all finite places not dividing $`\mathrm{}.`$

Here, we have used the fact one can find solvable extensions with prescribed local extensions (see for instance Lemma 2.2 of ).

It is now immediate that the result we want follows immediately from a higher weight version of the main theorem of . The proof of the main theorem of  for the higher weight case works in exactly the same way as for the weight 2 case. The only modification, or something that is to be checked, required is Lemma 2 of ; and, this can be found in  (with a slight modification, the result we need is Lemma 2, ibid.).  $`\mathrm{}`$

### 2.2

We now turn to the other serious issue of when the residual representation is modular. Conjecturally, the answer is always yes for odd, absolutely irreducible, continuous representations (Serre’s conjecture); our knowledge covers only a handful of residue fields.

###### Theorem 2.6

Let $`\overline{\rho }:G_{}GL_2(𝔽_5)`$ be an absolutely irreducible, continuous representation with determinant equal to $`ϵ_5^3(mod5)`$. Then $`\overline{\rho }`$ is modular.

Proof. Let $`\stackrel{~}{\rho }:=\overline{\rho }ϵ_5^1(mod5).`$ Then $`\stackrel{~}{\rho }`$ is a continuous Galois representation with values in $`GL_2(𝔽_5)`$ and determinant equal to the mod 5 cyclotomic character $`ϵ_5(mod5)`$. By Theorem 1.2 of , we can find an elliptic curve $`E`$ over $``$ such that $`\overline{\rho }_{E,5}`$, the Galois representation given by the 5-torsion points of $`E`$, is equivalent to $`\stackrel{~}{\rho }.`$ Since all elliptic curves over $``$ are modular (by ), it follows that $`\stackrel{~}{\rho }`$ is modular. The required result then follows. $`\mathrm{}`$

For Galois representations with values in $`GL_2(𝔽_7)`$, we have the following (see , and Theorem 9.1 of ):

###### Theorem 2.7

Let $`\overline{\rho }:G_{}GL_2(𝔽_7)`$ be an absolutely irreducible, continuous, odd representation. If the projective image of $`\overline{\rho }`$ is insoluble, we also assume that:

* The projective image of inertia at $`3`$ has odd order.
* The determinant of $`\overline{\rho }`$ restricted to the inertia group at $`7`$ has even order.

Then $`\overline{\rho }`$ is modular.

The result applies, for example, if $`\overline{\rho }`$ has determinant $`ϵ_7^3(mod7)`$ and is unramified at 3.

The two results above do not specify the weight, or the level. For the applications we have in mind, one needs to be able to produce newforms of the ‘right weight and right level’ giving rise to the residual representation $`\overline{\rho }.`$ In view of , we might as well assume that $`\overline{\rho }`$ is absolutely irreducible. And once we make this assumption, we can indeed produce newforms of the ‘right weight and right level’ (see Theorem 1.1 of ).

## 3 Proof of the main theorem

We now apply the results of the last section to the given rigid Calabi-Yau threefold $`X`$ defined over $``$.

### X has good reduction at 3 and 7

We consider the $`7`$-adic representation

$$\rho _{X,7}:G_{}GL_2(_7).$$

Note that it is crystalline at $`7`$, and unramified at $`3`$. We also know that it is absolutely irreducible.

If the residual representation is absolutely reducible, then $`\rho _{X,7}`$ is modular by Theorem 2.2. So suppose that the residual representation is absolutely irreducible. The residual representation is modular by Theorem 2.7. Moreover, we know (from ) that there is weight $`4`$ newform of level coprime to $`7`$ and $`3`$ which gives rise to $`\overline{\rho }.`$ The theorem in the ordinary case follows from Theorem 2.3.

Finally, suppose that we are in the crystalline but not ordinary case. Let $`\omega _2`$ denote the second fundamental character of the inertia group at $`7`$. We then have (cf. , Chapter 9)

$$\overline{\rho }_{X,7}|_{I_7}\left(\omega _2^3\omega _2^{7.3}\right),$$

and so the projectivization of the image of inertia is a cyclic group of order 8. One can then check the following: $`\overline{\rho }_{X,7}`$ restricted to $`\left(\sqrt{7}\right)`$ is irreducible. Making use of the (essential) fact that we are working with a prime as large as $`7`$, the description above of $`\overline{\rho }_{X,7}|_{I_7}`$ and the inequality $`(\mathrm{}+1)/\mathrm{gcd}(w,\mathrm{}+1)>2`$ valid for $`\mathrm{}=7`$ and $`w=3`$ ($`w`$ denotes the non-zero Hodge-Tate weight), one deduces the absolute irreducibility of $`\overline{\rho }`$ when restricted to the Galois group of $`_7(\sqrt{7})`$. The proof (for general $`\mathrm{}`$ and $`w`$) follows an idea of Ribet to deal with dihedral primes for Galois representations, and is given in full detail in  for the case $`\mathrm{}=3,w=1`$. Alternatively, one can manipulate in the group $`PSL_2(𝔽_7)`$ (which we leave for the interested reader).

Now take $`F`$ to be a totally real, even degree, solvable extension of $``$ in which $`7`$ splits completely and $`\overline{\rho }|_{G_F}`$ arises from a Hilbert modular form of level 1. This can be done by Theorem 2.5. Finally, we deduce that $`\rho `$ is modular by applying Theorem 2.4 (that $`\overline{\rho }`$ restricted to the absolute Galois group of $`F(\sqrt{7})`$ is irreducible follows from the preceding paragraph as $`7`$ splits completely in $`F`$).

### X has good reduction at 5

In this case, we make use of the $`5`$-adic representation $`\rho _{X,5}`$. As before, we know that $`\rho _{X,5}`$ is absolutely irreducible. Moreover, as before, we only need to consider the cases when $`\overline{\rho }_{X,5}`$ is absolutely irreducible. Using Theorem 2.6 and Theorem 1.1 of , we see that there is a newform of weight $`4`$ and level coprime to $`5`$ which gives rise to $`\overline{\rho }.`$ One then deals with the ordinary case as before using Theorem 2.3.

So suppose that we are in the crystalline but not ordinary case. The image of inertia at $`5`$ is then cyclic of order $`8`$; the image of a decomposition group at $`5`$ is non-abelian of order $`16.`$ Thus if $`F`$ is a totally real field in which $`5`$ splits completely, we will still have

$$\overline{\rho }_{X,5}|_{G_F}$$

absolutely irreducible.

Suppose that the restriction of $`\overline{\rho }_{X,5}`$ to the Galois group of $`G_{F(\sqrt{5})}`$ is absolutely reducible. Since $`F(\sqrt{5})`$ is totally real, this is the same as reducibility. In particular, we can assume that the image of $`\overline{\rho }_{X,5}(G_{F(\sqrt{5})})`$ is the subgroup of $`GL_2(𝔽_5)`$ consisting of elements

$$\left(\begin{array}{cc}x& 0\\ 0& \pm x^1\end{array}\right)\text{with}x𝔽_5^\times ,$$

and hence that the image of $`G_F`$ is generated by the above subgroup and $`\left(\begin{array}{cc}0& 1\\ 3& 0\end{array}\right).`$ It follows that elements with determinant equal to $`2`$ or $`3`$ have trace $`0`$.

We are now ready to make use of the condition that $`t_3(p)`$ is not divisible by 5. Choose an $`F`$ which is totally real and solvable as given by Theorem 2.5. We can choose such an $`F`$ with 5 and $`p`$ splitting completely in $`F`$. Since $`t_3(p)`$ is not divisible by 5, the preceding argument shows that $`F`$ satisfies both the conditions of Theorem 2.4. It follows that $`\rho _{X,5}`$ is modular.

###### Remark 3.1

We are grateful to Fred Diamond for pointing out that one could prove modularity without appealing to base change. The relevant result, dealing with modular representations over $``$, is proved in .

###### Remark 3.2

What we proved, purely in terms of Galois representations, is the following:
Let $`\mathrm{}=5`$ or $`7,`$ and let

$$\rho :G_{}GL_2(_{\mathrm{}}^{ac})$$

be an irreducible continuous representation, unramified outside finitely many primes, and having determinant $`ϵ_{\mathrm{}}^3`$. Assume the following:

1. $`\rho `$ is crystalline at $`\mathrm{}`$ with Hodge-Tate weights $`\{0,3\}`$.
2. The residual representation

$$\overline{\rho }:G_{}GL_2(𝔽_{\mathrm{}}^{ac})$$

takes values in $`GL_2(𝔽_{\mathrm{}}).`$
3. If $`\mathrm{}=7`$, then $`\rho `$ is unramified at $`3`$.
4. If $`\mathrm{}=5`$, then there is some prime $`p\pm 2(mod5)`$ where $`\rho `$ is unramified and the trace of Frobenius at $`p`$ is not divisible by 5.

Then $`\rho `$ is modular.

## 4 Applications to known examples

As mentioned in the introduction, all known rigid Calabi-Yau threefolds are modular. There are about thirty examples known; the levels for which one can construct a rigid Calabi-Yau (of that level) are

$$6,8,9,12,21,25,50,$$

a family coming from conifolds (see Section 5.4 of ), and those of type $`III_0`$ (see Section 5.5 of ) We are grateful to Helena Verrill and Noriko Yui for pointing these out; for details and equations for the rigid Calabi-Yau threefolds, see  and the references there. It is a pleasant surprise that the result of this article covers all known rigid Calabi-Yau threefolds except for the level 9 case.

Let us check that the hypotheses of Theorem 1.2 are satisfied by these known Calabi-Yau threefolds. In principle, we should write down explicit models and verify the conditions (for such explicit models, see ). However, we already know that these examples are modular—we just want to check that the result applies often. We get this information by looking at tables of newforms. What we mean is the following: let $`N`$ be a positive integer, and let $`CY(N)`$ be the set of rigid Calabi-Yau threefolds whose $`L`$-series (or $`q`$-series) expansions agree with newforms of weight 4, level $`N,`$ at least up to, say, twenty terms. We know from explicit calculations that if $`XCY(N),`$ then $`X`$ has good reduction outside primes dividing $`N.`$ To see if our result would apply to the threefolds in $`CY(N)`$, we need to see if either $`(21,N)=1`$ or $`5N.`$ In the second case, we would need to look at a few $`t_3(p)`$: we know how to calculate them, and they agree with what comes from modular forms.

For example, Theorem 1.2 with the first condition will apply to the cases for which the level comes out to be 8, 25 or 50. This is easy to check: for instance, the quintic of Chad Schoen given in section 5.1 of  is easily seen to have good reduction at 3 and 7. For the cases when the level is 6, 12, or 21, one looks at tables of newforms with weight 4 (see W. Stein’s website, ). We need only look for newforms with $`q`$-expansions having $``$-coefficients. We find one newform of level 6 (with $`t_3(7)=16`$), one of level 12 (with $`t_3(7)=8`$), and two of level 21 (they have $`t_3(13)=34,62`$ respectively); in all cases, we can apply Theorem 1.2 with the second set of conditions (the true values of these traces for the corresponding examples of rigid Calabi-Yau threefolds have been computed by many people and of course they agree with the above values).

We leave it to the reader to apply the result and check for modularity of the family coming from conifolds and those of type $`III_0`$ using the information given in Section 5.4 of .

###### Remark 4.1

Of course, our theorem does not provide any new examples of rigid Calabi-Yau threefolds over $`.`$ However, if more examples are found, our theorem seems simpler to apply than other results, and numerical evidence suggests that the hypotheses seem to be satisfied sufficiently often for the theorem to be genuinely useful. If an infinite family of rigid Calabi-Yau threefolds over $``$ were to be discovered, the theorem might apply to establish modularity for the family.

Current addresses:

L. Dieulefait,
Équipe de Théorie des Nombres, Institut de Mathématiques de Jussieu, Université Pierre et Marie Curie (Paris VI), Paris, France.
e-mail: luisd@math.jussieu.fr; ldieulefait@crm.es

J. Manoharmayum,
Department of Pure Mathematics, University of Sheffield, Sheffield S3 7RH, U.K.
e-mail: j.manoharmayum@sheffield.ac.uk