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# Schottky barrier heights at polar metal/semiconductor interfaces

## I Introduction

Metal/semiconductor (MS) interfaces have been the focus of extensive theoretical and experimental studies for several decades.Rhoderick-88 ; Brillson-92 ; Tung-92 ; Margaritondo-99  To date, however, we are still far from a complete understanding of the factors which control the Schottky barrier height (SBH) at these interfaces. In recent years, new research activities have been developed in the area of band engineering at MS interfacesFranceschi-98 ; Sorba-96 ; Orto-94 ; Cantile-94 ; Koyanagi-93 ; Costa-91  and on the properties of metal/wide-gap-semiconductor contacts.Lazzarino-98 ; Chen-94 ; Barinov-01  These developments have stimulated renewed interest in some basic issues concerning Schottky barriers, and in particular in the mechanisms that control the SBH dependence on bulk-semiconductor and interface-specific characteristics.

The problem of Schottky barrier formation has been traditionally addressed by studying the dependence of the SBH on the metal used in the junction.Monch-90  Early studies suggested a Schottky-Mott behavior controlled by the metal work function for highly ionic or wide-gap semiconductors, and a weak dependence on the metal type and on the junction fabrication method for the most covalent semiconductors, such as Si or GaAs.Brillson-92 ; Monch-90  The latter trend was generally attributed to various Fermi level pinning mechanisms, such as pinning by metal-induced-gap states (MIGS)Heine-65  at an intrinsic charge neutrality level of the semiconductorTersoff-84 ; Flores-87  or pinning by native defect states of the semiconductor at some extrinsic gap level.Spicer-93 ; Woodall-82  Furthermore, a correlation between Schottky barriers and heterojunction band offsets was observed experimentally for a number of systems,Margaritondo-87  and similarly ascribed to Fermi level pinning at a bulk reference level. Finally, the effect of the semiconductor ionicity on the SBH trend with the metal work function was examined in pioneering self-consistent studies of jellium/semiconductor contacts, and the trend could also be generally understood in terms of MIGS properties of the semiconductor.Louie-77

More recent experiments on metal contacts to covalent semiconductors, however, have revealed a much weaker electronic pinning than was previously believed.Brillson-92  In particular, there have been reports of considerable changes in metal/Si and metal/GaAs SBH’s obtained by altering the structural properties and/or the chemical composition of the interface.Sullivan-93 ; Cantile-94  The conclusion that the SBH does depend most generally on the microscopic atomic structure of the interface has been reached by many authors, both on experimentalBrillson-92 ; Tung-92 ; Franceschi-98 ; Sorba-96 ; Orto-94 ; Cantile-94 ; Lazzarino-98 ; Chen-94 ; Sullivan-93  and theoreticalLazzarino-98 ; Zhang-85 ; Dandrea-93 ; Charlesworth-94 ; Berthod-96 ; Ruini-97 ; Bardi-99  grounds. While opening a promising line of research on Schottky barrier engineering, these observations complicate seriously the search for simple models of Schottky barrier formation, since the inclusion of the interface atomic structure seems unavoidable.

Given the complexity and variety of the atomic structure at metal/semiconductor contacts, it seems unlikely that a simple unified model could emerge and entirely cover the various facets of Schottky barrier formation. Conversely, a systematic investigation of the problem starting from abrupt, defect free interfaces, and progressively introducing perturbations at the interface could help identifying relevant microscopic mechanisms and provide a firmer basis for modeling Schottky barrier properties. Progress in computational physics have made possible accurate ab initio calculations of the electronic structure of MS contacts, and the complexity of the systems which can be examined is steadily increasing; this type of computations can provide the means to carry out such an investigation and probe the correlation between microscopic atomic structures and SBH’s. The present study is a first step in this direction.

In this article, we study from first principles the dependence of the SBH on selected bulk and surface characteristics of the semiconductor, for a given metal. Specifically, we examine abrupt Al/$`X`$ (100) junctions, where $`X=`$ (Ge, GaAs, AlAs, and ZnSe) are lattice matched semiconductors of increasing ionicity, and we investigate the microscopic mechanisms responsible for the SBH changes with the semiconductor chemical composition and surface termination (cation or anion). A model based on a linear-response-theory scheme is then developed, which explains our ab initio results and SBH trends observed experimentally.

## II Method of calculation

We have carried out ab initio calculations, within the Local-Density Approximation (LDA) to Density Functional Theory (DFT), using the pseudopotential method.Pickett-89  We used norm-conserving scalar-relativistic Troullier-Martins pseudopotentialsTroullier-91 ; Pseudo  in the Kleinman-Bylander non-local formKleinman-82  and the exchange-correlation functional of Ceperley and Alder.Ceperley-80  The electronic states were expanded on a plane-wave basis set using a kinetic energy cut-off of 20 Ry. We used supercells containing 7 Al layers and 13 semiconductor layers ($`7+13`$ supercell) to model defect-free Al/$`X`$ (100) junctions. In section IV.2, we employed larger supercells ($`7+21`$) to investigate the screening of substitutional charges placed in the junctions, and to compute the parameters $`(D_s,\delta _s)`$ necessary to model this screening. All supercell calculations were performed with a (2, 6, 6) Monkhorst-Pack $`k`$-point grid.Monkhorst-76

We considered ideally abrupt epitaxial junctions and neglected atomic relaxation at the interfaces. The effect of atomic relaxation at the Al/GaAs (100) and Al/ZnSe (100) interfaces has been examined in Refs. Lazzarino-98,  and Berthod-98, . Atomic relaxation decreases (increases) the $`p`$-type Schottky barriers of the abrupt Al/GaAs (Al/ZnSe) junctions by 0–0.1 eVBerthod-98  (0.1–0.2 eVLazzarino-98 ; Berthod-99 ), and has no influence on the SBH ordering of the anion- and cation-terminated interfaces.

The epitaxial alignment of Al on the (100) surfaces of the four semiconductors under study is illustrated in Fig. 1(a). This type of alignment corresponds to the lattice-matching condition: $`a_{\text{Al}}=a/\sqrt{2}`$, where $`a`$ is the semiconductor lattice parameter. The Al  direction is parallel to the semiconductor  axis, and the whole Al fcc lattice is rotated by 45 about its  axis with respect to the semiconductor substrate. Experimentally — and also in our calculations — Ge, GaAs, AlAs, and ZnSe are lattice-matched semiconductors, and the equilibrium lattice constant of Al is slightly larger (1%) than $`a/\sqrt{2}`$. This results in a small compressive strain in the Al in-plane lattice parameter, which is accommodated by an elongation ($`3`$%) of the Al overlayer, assuming pseudomorphic conditions. For the semiconductor lattice parameter, we used the theoretical value $`a=5.55`$ Å ($`a^{\text{exp.}}=5.65`$ Å). The metal-semiconductor interlayer distance $`d`$ at the junction was taken as the average between the (100) interlayer spacings in the semiconductor and in the (strained) Al bulk parts, i.e., $`d=1.72`$ Å. The polar Al/$`X`$ (100) junction offers two inequivalent abrupt interfaces, either with anion- or cation-terminated semiconductor surface, which we both considered in our study \[see Fig. 1(b)\]. In what follows, we will refer to the anion- and to the cation-terminated interface as interface I and II, respectively.

To evaluate the $`p`$-type SBH, $`\varphi _p`$, we used the same approach as in previous studies:Berthod-96 ; Berthod-98

$$\varphi _p=\mathrm{\Delta }V+\mathrm{\Delta }E_p,$$
(1)
where $`\mathrm{\Delta }V`$ is the electrostatic-potential lineup at the interface and $`\mathrm{\Delta }E_p`$ is the difference between the Fermi level in the metal and the valence-band maximum (VBM) in the semiconductor, each measured with respect to the average electrostatic potential in the corresponding crystal. The band-structure term $`\mathrm{\Delta }E_p`$ is characteristic of the individual bulk crystals forming the junction. This term was computed using the Kohn-Sham (KS) eigenvalues of standard bulk band-structure calculations. The potential lineup $`\mathrm{\Delta }V`$ contains all interface-specific contributions to $`\varphi _p`$ and was obtained — via Poisson’s equation and using a macroscopic average techniqueBerthod-96 ; Berthod-98  — from the self-consistent supercell charge density.

For a meaningful comparison of our calculated SBH’s with experiment, $`\mathrm{\Delta }E_p`$ should include quasiparticle and spin-orbit corrections. The spin-orbit correction is simply $`+\frac{\mathrm{\Delta }_{\text{so}}}{3}`$, where $`\mathrm{\Delta }_{\text{so}}`$ is the total spin-orbit splitting at the semiconductor valence-band maximum, which was taken from experiment. For a metal, in principle, the exact KS Fermi energy and the quasiparticle Fermi energy must coincide at zero temperature.Dreizler-90  Furthermore, LDA calculations for the work functions of various Al surfaces performed with the same method and the same pseudopotentials as in the present study — and neglecting many-body corrections on the Al Fermi energy — yielded values which agree with the experimental data to within a few tenths of meV.Fall-98  In the present study, therefore, for the metal Fermi energy we just used the LDA result. The corrected band term is thus $`\mathrm{\Delta }E_p=\mathrm{\Delta }E_p^{\text{KS}}\mathrm{\Delta }E_{\text{qp}}\frac{\mathrm{\Delta }_{\text{so}}}{3}`$, where $`\mathrm{\Delta }E_p^{\text{KS}}`$ is the KS band term and $`\mathrm{\Delta }E_{\text{qp}}`$ is the difference between the quasiparticle and KS semiconductor VBM energies.

For the quasiparticle corrections, we used the results of GW calculations taken from the literature. For Al/GaAs we used the correction $`\mathrm{\Delta }E_{\text{qp}}^{\text{GaAs}}=0.36`$ eV evaluated by Charlesworth et al.,Charlesworth-94  who employed for the reference LDA calculations the same exchange-correlation potential as we do. For Ge (AlAs) we used the correction for GaAs, and the difference between the Ge (AlAs) and GaAs corrections evaluated in Ref. Zhu-91, , i.e., $`\mathrm{\Delta }E_{\text{qp}}^{\text{Ge}}\mathrm{\Delta }E_{\text{qp}}^{\text{GaAs}}=+0.09`$ eV ($`\mathrm{\Delta }E_{\text{qp}}^{\text{AlAs}}\mathrm{\Delta }E_{\text{qp}}^{\text{GaAs}}=0.11`$ eV).GWxc  The quasiparticle corrections to the band structure of ZnSe have been evaluated in Ref. Zakharov-94, . As the LDA bandgap in our calculations and in Ref. Zakharov-94,  are different, due to the different pseudopotentials employed, we took the valence-band-edge correction of Ref. Zakharov-94,  and scaled it by the ratio of the difference between the LDA and GW bandgap in the two calculations. The resulting estimate for $`\mathrm{\Delta }E_{\text{qp}}^{\text{ZnSe}}`$ is $`0.50`$ eV. Using the experimental spin-orbit splittings $`\mathrm{\Delta }_{\text{so}}^X=`$ 0.30, 0.34, 0.28, and 0.43 eV for $`X=`$ Ge, GaAs, AlAs, and ZnSe,Landolt-82  the total corrections are 0.17, 0.25, 0.36, and 0.36 eV, respectively.erratum  The numerical uncertainty on the absolute value of the SBH’s is estimated as $`0.1`$ eV for Al/Ge, Al/GaAs, and Al/AlAs, and as $`0.2`$ eV for Al/ZnSe. For a given interface geometry, however, the relative barrier values ($`\mathrm{\Delta }\varphi _p`$ in Table 2) are considerably more accurate, i.e, have an estimated numerical accuracy of $`50`$ meV.

## III Results for the Schottky barrier heights

The calculated SBH’s for the abrupt Al/$`X`$ (100) interfaces, including many-body and spin-orbit corrections, are given in Table 1. We observe a systematic difference between the type-I and type-II interfaces: the $`p`$-type SBH is always higher for the type-I (anion-terminated) interface. This difference increases with increasing semiconductor ionicity. Our theoretical results are compared with experimental SBH values in Fig. 2. For the Al/Ge, Al/GaAs, and Al/AlAs systems the experimental ranges correspond to data obtained by transport measurements. In the case of Al/GaAs, photoemission measurements — performed at low metal coverage — give rise to a wider range of SBH values,Brillson-93  but the scattering in the data decreases significantly when thick metallic overlayers are deposited and the barriers are measured by transport techniques. For Al/ZnSe we are not aware of any transport data and we used photoemission results.

In the case of Al/Ge, no SBH measurement has been performed, to our knowledge, on the (100)-oriented interface. In Fig. 2 we have thus used the existing transport dataThanailakis-73  on Al/$`n`$-Ge (111) junctions ($`\varphi _n=0.52`$–0.61 eV), together with the Ge experimental bandgap at room temperature, $`E_g^{\text{Ge}}=0.66`$ eV.Sze-81  The resulting barrier heights $`\varphi _p=0.05`$–0.14 eV compare reasonably well with our calculated value of 0.21 eV. In the case of Al/GaAs (100) the transport measurements give values of $`\varphi _p`$ between 0.58 eV and 0.76 eVCantile-94 ; Koyanagi-93 ; Costa-91 ; Johnson-76 ; Cho-78 ; Wang-83 ; Barret-83 ; Eglash-84 ; Waldrop-85 ; Missous-86 ; Eglash-87 ; Missous-90 ; Bosacchi-94  (we used $`E_g^{\text{GaAs}}=1.42`$ eV to estimate the $`p`$-type barrier heights from measurements performed on Al/$`n`$-GaAs junctions). This is in relatively good agreement with our calculated SBH of 0.76 eV for the Ga-terminated interface, and still consistent with our value of 0.86 eV for the As-terminated interface. Concerning the effect of the GaAs-surface stoichiometry on the measured SBH, we note that different conclusions have been reached by different groups. Some studies, including Refs. Cho-78,  and Wang-83, , have found a small ($`0.1`$ eV) difference between the SBH’s measured in junctions fabricated on As-rich and on Ga-rich surfaces (As-rich leading to higher $`\varphi _p`$, consistent with our results), while other studies, such as Refs. Barret-83,  and Missous-86, , found no difference.

For the Al/AlAs system, Ref. Wang-83,  reports SBH values for Al/$`n`$-AlAs (100) ranging from 0.85 to 0.94 eV for various reconstructions of the semiconductor surface, while somewhat higher values, 0.95 and 1.01 eV, have been given in Refs. Missous-90,  and Bosacchi-94, , respectively. Using the experimental bandgap $`E_g^{\text{AlAs}}=2.16`$ eV, the resulting range is $`\varphi _p=1.15`$–1.31 eV, in good agreement with the calculated SBH for the Al-terminated AlAs surface (1.16 eV), and somewhat smaller than the value we find for the As-terminated surface (1.45 eV). The Al/$`n`$-ZnSe (100) SBH has been investigated in Refs. Lazzarino-98, , Chen-94, , and Vos-89,  for different reconstructions of the ZnSe (100) surface. Very similar values have been reported for the $`c(2\times 2)`$ and $`2\times 1`$ reconstructions, namely $`\varphi _p=2.12`$–2.15 eVLazzarino-98 ; Chen-94 ; Vos-89  and $`\varphi _p=2.11`$–2.15 eV,Lazzarino-98 ; Chen-94  respectively, while a lower SBH, $`\varphi _p=1.91`$ eV, has been measured for the $`1\times 1`$ reconstruction.Lazzarino-98  These values are in between our values of 1.82 eV for the Zn-terminated and of 2.18 eV for the Se-terminated interface.

The general agreement between theory and experiment in Fig. 2 indicates that our calculations for ideal MS structures (abrupt interfaces with no atomic relaxation) capture the general trend of the SBH with the chemical composition of the semiconductor. We note that for Al/ZnSe, the inclusion of the appropriate reconstruction and relaxation brings the theoretical results in very close agreement with the experimental values.Lazzarino-98

## IV Interpretation and models

### IV.1 General trend with the semiconductor chemical composition

Experimentally a correlation was found between Schottky barriers and heterojunction band offsets.Margaritondo-87  A large number of MS contacts and semiconductor heterojunctions were shown to verify, within 0.4 eV, the transitivity relationship:

$$\varphi _p[M/S_1]\varphi _p[M/S_2]=\mathrm{\Delta }E_{\text{VBO}}[S_1/S_2],$$
(2)
where $`M`$ is a metal (such as Al or Au; in general neither a highly reactive nor a transition metalReactive ), $`S_1`$ and $`S_2`$ are two semiconductors, and $`\mathrm{\Delta }E_{\text{VBO}}[S_1/S_2]`$ is the corresponding valence-band offset (VBO). This correlation was most often observed for MS junctions used in transport measurements, i.e., which had been annealed for fabrication of the contacts. The experimental data in Fig. 2 are in general agreement with the above empirical transitivity rule.

We note that the transitivity rule, as formulated in Eq. (2), disregards any dependence of the SBH on the microscopic interface structure, and cannot therefore give a complete account of the theoretical results in Fig. 2. Also, recent theoretical and experimental studies have shown that the band offset at heterovalent semiconductor heterojunctions depends critically on the orientation and other microscopic details of the interface.Baroni-89 ; Peressi-98 ; Franciosi-96  The right-hand side of Eq. (2) is thus ill defined, in general, for heterovalent semiconductors.

In this section we concentrate on the average SBH $`\overline{\varphi }_p=\frac{1}{2}\left(\varphi _p^\text{I}+\varphi _p^{\text{II}}\right)`$ of the abrupt, defect-free type-I and II interfaces, and propose a model for its variation with the semiconductor chemical composition, derived from an atomic-scale approach. We show that this variation is controlled essentially by the same bulk mechanism that determines band offsets at non-polar, defect-free semiconductor heterojunctions.Baroni-89  The splitting $`\mathrm{\Delta }\varphi _p=\varphi _p^\text{I}\varphi _p^{\text{II}}`$ due to the semiconductor-surface termination will be the focus of the next section.

Similarly to the SBH, the VBO may be written as: $`\mathrm{\Delta }E_{\text{VBO}}=\mathrm{\Delta }E_v+\mathrm{\Delta }V`$, where $`\mathrm{\Delta }E_v`$ is the difference between the VBM energies of the two semiconductors, each measured relative to the mean electrostatic potential in the corresponding crystal, and $`\mathrm{\Delta }V`$ is the electrostatic potential lineup at the interface. Since the band-structure terms $`\mathrm{\Delta }E_v`$ and $`\mathrm{\Delta }E_p`$ \[in Eq. (1)\] are differences between bulk values of the individual crystals forming the junction, they verify by definition the transitivity relationship in Eq. (2). All non transitive contributions are contained thus in the potential lineup terms $`\mathrm{\Delta }V`$.

In the case of semiconductor heterojunctions a linear-response-theory (LRT) approach, which focuses on $`\mathrm{\Delta }V`$ and treats the interface as a perturbation with respect to a bulk reference system, has provided an accurate general description of band-offset trends.Baroni-89 ; Peressi-98  Based on this approach and comparision with fully self-consistent ab initio calculations, it has been shown, in particular, that in the case of defect-free, isovalent lattice-matched semiconductor heterojunctions, $`\mathrm{\Delta }V`$ is determined by the properties of the bulk constituents (as opposed to interface-specific features, such as interface orientation or interface abruptness). Specifically, if $`S_1`$ and $`S_2`$ are the two semiconductors, with anion (cation) species $`a_1`$ ($`c_1`$) in $`S_1`$ and $`a_2`$ ($`c_2`$) in $`S_2`$, the potential lineup is given within LRT by:Baroni-89

$$\mathrm{\Delta }V\left[S_1/S_2\right]=\frac{2\pi e^2}{3\mathrm{\Omega }}r^2\left[\mathrm{\Delta }n_a(𝒓)+\mathrm{\Delta }n_c(𝒓)\right]𝑑𝒓,$$
(3)
where the integration is over the whole space, $`\mathrm{\Omega }`$ is the volume of the bulk unit cell, and $`\mathrm{\Delta }n_a`$ ($`\mathrm{\Delta }n_c`$) is the electronic charge density induced by a single anion (cation) substitution $`a_1a_2`$ ($`c_1c_2`$) in the bulk semiconductor $`S_1`$.origin  Based on this LRT approach, it has also been shown that in the case of heterovalent lattice matched semiconductors, Eq. (3) also applies in the specific case of defect-free interfaces with the non-polar (110) orientation.Peressi-98

Using a similar linear-response scheme for $`\mathrm{\Delta }V`$, we show in Appendix A that the average SBH $`\overline{\varphi }_p`$ can be described by the following model:

$$\overline{\varphi }_p^{\text{mod}}=\varphi _p\left[\text{Al}/X(100)\right]+\mathrm{\Delta }E_{\text{VBO}}\left[X/X(110)\right].$$
(4)
The first term on the right-hand side of Eq. (4) is the SBH at the (100) interface between Al and the group-IV virtual crystal, denoted $`X`$, which is obtained by averaging the anion and cation pseudopotentials of the III-V or II-VI compound $`X`$ ($`X=`$ GaAs, AlAs, ZnSe). The second term is the VBO of the non-polar $`X`$/$`X`$ (110) heterojunction.

The basic approximation to derive Eq. (4) is to construct the charge densities of the Al/$`X`$ I and II junctions (and hence their average lineup) starting from the reference Al/$`X`$ system, by adding a linear superposition of the charge densities induced in the virtual crystal $`X`$ by single anion and cation substitutions that transform $`X`$ into $`X`$. The Al/$`X`$ (100) junction is an optimal reference system in this context, which minimizes the deviations of $`\overline{\varphi }_p`$ from $`\overline{\varphi }_p^{\text{mod}}`$ in Eq. (4); these deviations vanish to the first order in the ionic substitutions which transform Al/$`X`$ into the Al/$`X`$ I and II junctions.

It is also possible to use as a reference system another Al/group-IV (100) junction, whose density is sufficiently close to the average density of the Al/$`X`$ I and II junctions. For instance, one may use Al/Ge as a common reference system and obtain (Appendix A):

$$\overline{\varphi }_p^{\text{mod}^{}}=\varphi _p\left[\text{Al}/\text{Ge}(100)\right]+\mathrm{\Delta }E_{\text{VBO}}\left[\text{Ge}/X(110)\right].$$
(5)
The deviations of $`\overline{\varphi }_p`$ from $`\overline{\varphi }_p^{\text{mod}^{}}`$ in Eq. (5) include, in this case, a first order correction in the substitutions. The latter correction can be identified with the dipole induced in the reference Al/Ge (100) junction by isovalent Ge $`X`$ substitutions performed within the first one to three Ge atomic layers closest to the interface (see Appendix A); such a dipolar term is generally small for isovalent substitutions ($`0.1`$ eV or less, see Ref. Bardi-99, ), and will be neglected here.

In Fig. 3 we compare graphically the model predictions, Eq. (4) and Eq. (5), with the calculated average SBH of the Al/$`X`$ I and II interfaces. The (110) VBO’s have been computed using supercells containing 8 planes of each semiconductor in the ideal (unrelaxed) lattice-matched geometry. The same energy cutoffs and $`k`$-points grids have been used as in the calculations of the Schottky barriers. The SBH of the Al/$`X`$ (100) junctions have been obtained using the same parameters as for the Al/$`X`$ (100) I and II interfaces. The results in Fig. 3 show that Eq. (4) and Eq. (5) provide a fairly accurate ($`\pm 0.15`$ eV) description of the average SBH $`\overline{\varphi }_p`$. We note that the SBH’s at the Al/$`X`$ junctions are all small, due to the small bandgaps of the virtual crystals ($`<0.4`$ eV), and similar to the LDA SBH at the Al/Ge (100) interface (0.04 eV). The results in Fig. 3 show that the (110) VBO — a bulk-related quantity in our calculations — controls the general increase of the barriers from the group-IV to the III-V and to the II-VI semiconductors.

### IV.2 Effect of surface termination

We will show here that the difference $`\mathrm{\Delta }\varphi _p=\varphi _p^\text{I}\varphi _p^{\text{II}}`$ due to the semiconductor-surface termination in Fig. 2 — and in particular the fact that the SBH is systematically higher for the anion than for the cation termination — can be understood in terms of surface-charge and image-charge effects. The mechanism is illustrated in Fig. 4.

With respect to the Al/$`X`$ interface, the ionic charge distributions of the interfaces I and II are obtained by substituting an anion (charge $`+\overline{\sigma }`$) on each anionic site and a cation (charge $`\overline{\sigma }`$) on each cationic site, as indicated in Fig. 4(a). For the III-V and II-VI compounds we have $`\overline{\sigma }=1`$ and $`\overline{\sigma }=2`$, respectively, in units of charge per unit-cell surface in the (100) plane. The arrows in Fig. 4(a) represent opposite delta functions on each anionic and cationic (100) plane, corresponding to the planar average of the ionic point-charge density. The macroscopic averageBaroni-89 ; Peressi-98  of this ionic charge distribution is represented in Fig. 4(b). In the bulk semiconductor, the macroscopic average eliminates the atomic-scale oscillations of the planar charge density; at the interface, however, a positive (negative) charge density subsists in the junction I (II). This macroscopic charge has a density $`\rho =\pm 2\overline{\sigma }/a`$ and extends over a distance $`a/4`$ between the last Al plane and the first semiconductor plane. It is therefore equivalent to a surface charge of density $`\sigma =\pm \overline{\sigma }/2`$.

Within a classical macroscopic description, a plane of charge in a semiconductor is screened by the dielectric constant $`ϵ_{\mathrm{}}`$ of the host material. Furthermore, in the presence of a metal the screened surface charge is neutralized by an image charge induced at the metal surface, and a potential difference is thus established between the two charges \[see Fig. 4(c)\]. If $`\sigma `$ is the density of surface charge in the semiconductor, $`x`$ the position of the plane of surface charge, and $`x_i`$ the position of the metal surface or image charge, the potential difference obtained from classical electrostatics is:

$$\mathrm{\Delta }U(x,\sigma )=4\pi e^2\frac{\sigma }{ϵ_{\mathrm{}}}(xx_i).$$
(6)
As can be seen from Fig. 4(c), in the junction I such a dipole lowers the average potential energy in the semiconductor with respect to its value in the metal, increasing the SBH $`\varphi _p`$; conversely, in the junction II the dipole raises the average potential in the semiconductor, decreasing $`\varphi _p`$. The mechanism illustrated in Fig. 4 thus provides a qualitative explanation for the difference between the SBH’s of the interfaces I and II. Of course, the classical limit given by Eq. (6) is expected to be correct only for a charge placed at a large distance from the metal. As we will see below, however, closer to the metal the above type of description may still be used provided the inhomogeneous nature of the screening near the metal is taken into account.

To check that the mechanism in Fig. 4 can indeed account for the SBH differences $`\mathrm{\Delta }\varphi _p`$, we have calculated the changes in the lineup (and hence in the SBH) induced by surface charges of varying magnitude, placed on the semiconductor plane closest to the metal in the Al/$`X`$ I and II junctions. At the interface I (II), a surface charge of density $`|\sigma |`$ ($`+|\sigma |`$) was introduced by replacing the anion A (cation C) of the semiconductor layer adjacent to the metal surface by a virtual ion $`\text{A}_{1\frac{\sigma }{2}}\text{C}_{\frac{\sigma }{2}}`$ ($`\text{C}_{1\frac{\sigma }{2}}\text{A}_{\frac{\sigma }{2}}`$). The resulting changes $`\mathrm{\Delta }U`$ in the SBH obtained from the ab initio calculations are shown in Fig. 5. The negative (positive) surface charge decreases (increases) the $`p`$-type SBH of the anion-terminated (cation-terminated) interfaces, consistent with the screened surface charge and image charge description in Fig. 4(c). We also note that, consistent with the latter description, the bare monopole is replaced by an interface dipole in the multipole expansion of the total (electronic plus ionic) charge disturbance.

The macroscopic average of the difference between the ionic potentials in the junctions II and I, in Fig. 4(a), is equivalent to a surface charge $`\sigma =1`$ at the interface for the III-V semiconductors and $`\sigma =2`$ for the II-VI semiconductors. Therefore, focusing on the effect of the macroscopic charges only and to the first order in the perturbation, the modification of the SBH in the junctions I for $`\sigma =1`$ ($`2`$) should be equal to the difference $`\varphi _p^{\text{II}}\varphi _p^\text{I}`$ for the III-V (II-VI) semiconductors. Similarly, the change of the SBH in the junctions II induced by a surface charge $`\sigma =+1`$ ($`+2`$) should be equal to $`\varphi _p^\text{I}\varphi _p^{\text{II}}`$. Our ab initio results in Fig. 5 show, however, that the responses $`\mathrm{\Delta }U`$ of the two interfaces are not linear when $`|\sigma |0.5`$ and differ in magnitude. Therefore, we take the average $`\overline{\mathrm{\Delta }U}`$ between the potential differences induced in the junctions I and II as our estimate for the difference $`\mathrm{\Delta }\varphi _p`$. The results are shown in Table 2. For Al/ZnSe we reported the calculated SBH changes for $`\sigma =\pm 2`$ (not shown in Fig. 5). The average values $`\overline{\mathrm{\Delta }U}`$ are seen to describe well the calculated difference $`\mathrm{\Delta }\varphi _p`$ and also the increase of $`\mathrm{\Delta }\varphi _p`$ when the semiconductor ionicity increases.

Although this supports the surface charge and image charge picture in Fig. 4(c), Eq. (6) needs to be revisited for charges placed close to the metal surface. For example, in the case of a test charge $`\sigma =0.1`$ on the first semiconductor layer, we obtain from Eq. (6) a potential difference $`\mathrm{\Delta }U=82`$ meV, using for the distance $`xx_i`$ the value $`d/2`$, where $`d=1.72`$ Å is the interplanar distance at the interface (see Fig. 1), and for $`ϵ_{\mathrm{}}`$ the theoretical dielectric constant of GaAs, $`ϵ_{\mathrm{}}^{\text{GaAs}}=12.4`$.Berthod-96  This result is more than 5 times larger than the ab initio result for the potential difference obtained for Al/GaAs and shown in Fig. 5.

In Ref. Berthod-96,  we observed a somewhat similar behavior in the case of local dipoles inserted in the Al/GaAs (100) junction. In the latter case, ab initio calculations were performed to determine the change in the lineup $`\mathrm{\Delta }u`$ induced by a dipole layer (i.e., two test charges $`+\sigma `$ and $`\sigma `$ placed on two adjacent cation-anion planes) introduced at various distances $`x`$ from the metal, within the semiconductor. In this numerical experiment, the bare dipole perturbation is $`\mathrm{\Delta }u_b=4\pi e^2\sigma l`$, where $`l`$ is the separation between the charged planes, and from the computed $`\mathrm{\Delta }u`$ we could directly measure the effective dipole screening $`ϵ_{\text{eff}}^{\text{dip}}=\mathrm{\Delta }u_b/\mathrm{\Delta }u`$ as a function of the dipole position $`x`$ in the junction. This screening was found to be strongly inhomogeneous and to increase exponentially as the dipole was approaching the metal surface. This was attributed to the MIGS tails and their high polarizability in the interface region. We also proposed a model for $`ϵ_{\text{eff}}^{\text{dip}}`$ which proved very accurate to describe the SBH changes $`\mathrm{\Delta }u(x,\sigma )`$ in the linear-response regime (i.e., to the first order in $`\sigma `$):Berthod-96

$$ϵ_{\text{eff}}^{\text{dip}}(x)ϵ_{\mathrm{}}+4\pi e^2D_s(E_\text{F},x)\delta _s.$$
(7)
Here $`D_s(E_\text{F},x)`$ is the MIGS surface density of states at the Fermi energy and at the position $`x`$ of the dipole, and $`\delta _s`$ is the decay length of the MIGS. The model Eq. (7) is also consistent with earlier MIGS-based model descriptions of Schottky barrier properties.Cowley-65 ; Louie-77 ; Zhang-85

In order to predict, in general, the effect of the surface termination in MS junctions, we would like to develop a model for $`\mathrm{\Delta }U`$ that takes into account the inhomogeneous nature of the electronic screening in the MIGS region and that is consistent with our previous results on the effect of the dipole layers on the SBH. In particular, this model should be consistent with the fact that, in the linear-response regime (small $`|\sigma |`$), the sum of the SBH modifications induced separately by two charges $`+\sigma `$ and $`\sigma `$ separated by a small distance $`l`$, $`\mathrm{\Delta }U(xl/2,\sigma )`$ and $`\mathrm{\Delta }U(x+l/2,\sigma )`$, respectively, must be equal to the SBH modification induced by the corresponding dipole:

$$\mathrm{\Delta }U(xl/2,\sigma )\mathrm{\Delta }U(x+l/2,\sigma )=\frac{4\pi e^2\sigma l}{ϵ_{\text{eff}}^{\text{dip}}(x)}.$$
(8)
Expanding the left-hand side of Eq. (8) to the first order in $`l`$, we obtain the differential equation:

$$\frac{\mathrm{\Delta }U}{x}(x,\sigma )=\frac{4\pi e^2\sigma }{ϵ_{\text{eff}}^{\text{dip}}(x)}.$$
(9)
With our expression for $`ϵ_{\text{eff}}^{\text{dip}}(x)`$ in Eq. (7) and a surface density of states that decays exponentially,exponential  $`D_s(E_\text{F},x)=D_s(E_\text{F},\mathrm{\hspace{0.17em}0})\mathrm{exp}(x/\delta _s)`$, the solution of Eq. (9) with the boundary condition $`\mathrm{\Delta }U(x_0)=0`$ is:

$$\mathrm{\Delta }U(x,\sigma )=4\pi e^2\frac{\sigma }{ϵ_{\mathrm{}}}\left[xx_0\delta _s\mathrm{log}\frac{ϵ_{\text{eff}}^{\text{dip}}(x_0)}{ϵ_{\text{eff}}^{\text{dip}}(x)}\right],$$
(10)
where $`x`$ is the position of the surface charge. We note that for large values of $`x`$, we recover the classical limit given by Eq (6), with $`x_i=x_0+\delta _s\mathrm{log}[ϵ_{\text{eff}}^{\text{dip}}(x_0)/ϵ_{\mathrm{}}]`$.

With the exception of $`x_0`$, all parameters necessary to evaluate $`\mathrm{\Delta }U(x,\sigma )`$ in Eq. (10) can be obtained straightforwardly from ab initio calculations performed either for the bulk semiconductor ($`ϵ_{\mathrm{}}`$) or for the unperturbed Al/$`X`$ junction (the MIGS-related parameters). In Table 2, we have reported our calculated values for the MIGS parameters $`D_sD_s(E_\text{F},\mathrm{\hspace{0.17em}0})`$ and $`\delta _s`$. These quantities were obtained from the calculated macroscopic average of the local density of states, $`N(E,x)`$, as $`D_s=_0^{\mathrm{}}N(E_\text{F},x)𝑑x`$ and $`\delta _s=\frac{1}{D_s}_0^{\mathrm{}}xN(E_\text{F},x)𝑑x`$, where the origin ($`x=0`$) was taken as the midpoint between the last Al and the first semiconductor plane, and $`\mathrm{}`$ indicates a position well inside the semiconductor (the center of the semiconductor slab in the supercell) where the MIGS vanish. As the values of $`D_s`$ and $`\delta _s`$ are slightly different for the interfaces I and II, we reported in Table 2 the average between the values calculated for the two interfaces.Previous\_delta\_s

In order to obtain an estimate for $`x_0`$, and also to test the model in Eq. (10), we have investigated ab initio the spatial dependence of $`\mathrm{\Delta }U`$ in the linear-response regime by introducing a small test surface charge $`\sigma =\pm 0.05`$ in the As-terminated Al/GaAs junction at different distances from the interface. This was done by replacing single layers of As (Ga) ions by virtual $`\text{As}_{0.95}\text{Si}_{0.05}`$ ($`\text{Ga}_{0.95}\text{Si}_{0.05}`$) anions (cations). As an example, we show in Fig. 6 the ab initio results for the charge density and potential induced by such a test charge on the sixth semiconductor layer from the metal. The macroscopic averages of the ionic, electronic, and total charge densities are displayed in Fig. 6(a). We have used a Gaussian filter function with full width at half maximum $`a/2`$ for the macroscopic average. This allows one, in particular, to distinguish the image charge contribution to the total charge density, close to the Al surface. The macroscopic average of the induced total electrostatic potential is displayed in Fig. 6(b). The corresponding potential difference is $`\mathrm{\Delta }U=0.24`$ eV.

In Fig. 6(c) we have plotted the discontinuity $`|\mathrm{\Delta }U|`$ induced by the test charge as a function of its position in the Al/GaAs junction. With the theoretical dielectric constant of GaAs ($`ϵ_{\mathrm{}}^{\text{GaAs}}=12.4`$) and the calculated values of $`D_s`$ and $`\delta _s`$ given in Table 2, the best fit of Eq. (10) to the data in Fig. 6(c) is obtained with $`x_0=0.6`$ Å. The model results obtained from Eq. (10) using $`x_0=0.6`$ Å have been reported in Fig. 6(c), and compare well with the results of the self-consistent calculations as a function of the distance.

Having a reasonable estimate for $`x_0`$ we may now use Eq. (10) to obtain also an estimate for the difference between the SBH’s of the interfaces I and II. As we have seen before, this difference may be evaluated as the potential change induced, to the first order, by a surface charge $`\overline{\sigma }=1`$ ($`2`$) per unit-cell surface on the first plane of the III-V (II-VI) semiconductor, i.e., at a position $`x=d/2`$ with $`d=1.72`$ Å (see Fig. 1). The resulting estimate $`\mathrm{\Delta }\varphi _p^{\text{mod}}`$ for the difference $`\mathrm{\Delta }\varphi _p`$ is thus

$$\mathrm{\Delta }\varphi _p^{\text{mod}}=4\pi e^2\frac{\overline{\sigma }}{ϵ_{\mathrm{}}}\left[d/2x_0\delta _s\mathrm{log}\frac{ϵ_{\text{eff}}^{\text{dip}}(x_0)}{ϵ_{\text{eff}}^{\text{dip}}(d/2)}\right].$$
(11)
The results obtained with this model are displayed in Table 2. To evaluate $`\mathrm{\Delta }\varphi _p^{\text{mod}}`$, we have used the theoretical value of the semiconductor dielectric constant $`ϵ_{\mathrm{}}^X`$ ($`X=`$ GaAs, AlAs, and ZnSe),diel  the surface density of states $`D_s`$ and MIGS decay length $`\delta _s`$ given in Table 2 for the Al/GaAs, Al/AlAs and Al/ZnSe junctions, and $`x_0=0.6`$ Å for all systems. The model results, in Table 2, yield the correct trend and order of magnitude for the difference between the SBH’s. We note that decreasing $`x_0`$ increases $`\mathrm{\Delta }\varphi _p^{\text{mod}}`$, but does not affect the trend. The same conclusion applies when a possible change in $`x_0`$, from GaAs to AlAs and to ZnSe, is taken into account by scaling the $`x_0`$ value obtained for GaAs with the ratio of the MIGS decay length, i.e., $`\delta _s^X/\delta _s^{\text{GaAs}}`$.x0\_depend

Although the present model approach provides a consistent picture of the effect of selected perturbations at MS interfaces, we would like to caution the reader that our model description applies to unrelaxed interfaces. In this connection it should be pointed out that a LRT model (based on dynamical effective charges) is available in the literature for quantitative predictions of the atomic relaxation contribution to the SBH.Ruini-97

## V Conclusion

Using a first-principle pseudopotential approach, we have investigated the Schottky barrier heights of abrupt lattice-matched Al/Ge, Al/GaAs, Al/AlAs, and Al/ZnSe (100) junctions, and their dependence on the semiconductor chemical composition and surface termination. The sensitivity of the SBH to microscopic interface features reveals the limits of the currently accepted semiempirical models of Schottky barriers. Such model theories generally neglect the effects of the microscopic interfacial morphology. This is due in part to the complexity of the actual atomic structure of most MS contacts, and also to the relatively limited information available on the atomic-scale geometry of buried interfaces.

Based on our ab initio studies, we have derived models which explicitly include the effects of the interface atomic structure in the case of some prototype defect-free, lattice-matched geometries. These models retain, within specific ranges of applicability, the same accuracy as the ab initio calculations. They show, in particular, that while the variation of the average SBH of the abrupt, anion- and cation-terminated Al/semiconductor (100) interfaces can be explained mainly in terms of the bulk properties of the semiconductors, the difference between the barrier heights of the anion- and cation-terminated interfaces results from a microscopic dipole generated by the screened charge of the polar semiconductor surface and its image charge at the metal surface. Our atomic-scale computations have also allowed us to show how the classical image charge concept, valid for charges placed at large distances from the metal, can be extended to distances shorter than the decay length of the metal-induced-gap states.

###### Acknowledgements.

One of us (CB) acknowledges support by the Swiss National Science Foundation under Grant N 20-47065.96. The computations were performed at the CSCS in Manno.

## Appendix A Model for the average SBH of the anion- and cation-terminated interfaces

In order to explain the behavior of the average SBH $`\overline{\varphi }_p`$ with the semiconductor composition, we have extended to MS contacts a linear-response-theory approach commonly used to study band offsets at semiconductor heterojunctions.Baroni-89 ; Peressi-98  The present analysis is also an extension to heterovalent semiconductors of an approach outlined in Ref. Bardi-99,  to model the Schottky-barrier changes with the alloy composition in Al/Ga<sub>1-x</sub>Al<sub>x</sub>As junctions.

We are interested in the average potential lineup $`\overline{\mathrm{\Delta }V}=\frac{1}{2}\left(\mathrm{\Delta }V^\text{I}+\mathrm{\Delta }V^{\text{II}}\right)`$, where $`\mathrm{\Delta }V^{\text{I(II)}}`$ is the potential lineup at the interface I (II), for which we want to establish the following model:

$$\overline{\mathrm{\Delta }V}\mathrm{\Delta }V\left[\text{Al}/Y(100)\right]+\mathrm{\Delta }V\left[Y/X(110)\right].$$
(12)
The first term on the right-hand side of Eq. (12) is the potential lineup at the reference (100) junction between Al and a group-IV (real or virtual) crystal $`Y`$ (e.g., the virtual crystal $`X`$ or Ge), having a charge density close to the average charge density of the Al/$`X`$ I and II junctions. The second term is the lineup at the non-polar (110) interface between the group-IV crystal $`Y`$ and the semiconductor $`X`$. To derive Eq. (12), we write the self-consistent electrostatic potential at the Al/$`X`$ (100) I (II) junction as

$$V^{\text{I(II)}}(𝒓)=V_0(𝒓)+V_1^{\text{I(II)}}(𝒓),$$
(13)
where $`V_0(𝒓)`$ is the electrostatic potential at the Al/$`Y`$ (100) junction. The average lineup $`\overline{\mathrm{\Delta }V}`$ can be expressed, according to Eq. (13), as $`\overline{\mathrm{\Delta }V}=\mathrm{\Delta }V_0+\mathrm{\Delta }V_1`$, where $`\mathrm{\Delta }V_0\mathrm{\Delta }V\left[\text{Al}/Y(100)\right]`$ and $`\mathrm{\Delta }V_1`$ is the lineup of the potential

$$V_1(𝒓)=\frac{1}{2}\left[V_1^\text{I}(𝒓)+V_1^{\text{II}}(𝒓)\right].$$
(14)
The potential $`V_1^{\text{I(II)}}`$ is the self-consistent electrostatic potential induced in the Al/$`Y`$ (100) junction by the ionic substitutions, $`Y`$ anion and $`Y`$ cation, performed in the semiconductor, which transform the Al/$`Y`$ system into the type-I (type-II) Al/$`X`$ system. Thus $`V_1^\text{I}`$ and $`V_1^{\text{II}}`$ have long-range contributions associated with each heterovalent anion and cation substitution in the group-IV crystal. These long-range terms cancel out in the average in Eq. (14), since each anion (cation) substitution in $`V_1^\text{I}`$ is compensated by a cation (anion) substitution associated with the same site in $`V_1^{\text{II}}`$. The average potential $`V_1`$ has therefore a well defined macroscopic average in the semiconductor, which is equal to $`\mathrm{\Delta }V_1`$, since $`V_1(𝒓)`$ vanishes in the metal.

One may thus evaluate $`\mathrm{\Delta }V_1`$ using a perturbative approach neglecting inter-site interactions in the ionic substitutions, because of the short-ranged nature of the potentials associated with each individual site. Within this approximation, $`V_1`$ is given by i) the superposition of the potentials induced by isolated anion and cation substitutions in the bulk crystal $`Y`$ plus ii) a correction due to the deviations from the bulk response for substitutions performed near the MS interface.

By construction, the potential lineup obtained from i) is orientation independent and equal to the potential lineup $`\mathrm{\Delta }V^{}\left[Y/X(110)\right]`$ at the non-polar $`Y/X`$ (110) interface, built from a superposition of the same isolated charge-density responses on one side of the $`X`$ (110) homojunction. Furthermore, previous ab initio and LRT studies of semiconductor heterojunctions have shown that the deviation of the lineup $`\mathrm{\Delta }V`$ (110) from the transitivity rule, and hence from $`\mathrm{\Delta }V^{}`$ (110), is typically less than 0.1 eV in IV-IV/III-V junctions, and of the order of 0.1 eV in IV-IV/II-VI junctions.Baroni-89 ; Peressi-98  We may therefore replace $`\mathrm{\Delta }V^{}\left[Y/X(110)\right]`$ by $`\mathrm{\Delta }V\left[Y/X(110)\right]`$ to obtain the contribution from i) to $`\mathrm{\Delta }V_1`$.

The correction to the lineup induced by ii) is given, to the first order in the substitutions, by $`\mathrm{\Delta }V_{\text{corr.}}=_id_i`$, where $`d_i=4\pi e^2𝑑xx\mathrm{\Delta }n_i(x)`$ is the dipole, and $`n_i(x)`$ the charge density, induced by the $`Y`$ anion or $`Y`$ cation layer substitution within the $`i^{\text{th}}`$ atomic plane from the interface in the Al/$`Y`$ junction. In practice, the dipoles $`d_i`$ vanish beyond the $`3^{\text{rd}}`$ to $`4^{\text{th}}`$ atomic plane from the junction, and $`\mathrm{\Delta }V_{\text{corr.}}`$ is generally of the order of 0.1 eV for isovalent substitutions.Bardi-99  Furthermore, when the Al/$`X`$ junction is used as a reference system, $`\mathrm{\Delta }V_{\text{corr.}}`$ exactly vanishes, because the corrections are opposite in the I and II junctions and cancel out in the average leading to $`\mathrm{\Delta }V_1`$. The correction $`\mathrm{\Delta }V_{\text{corr.}}`$ is therefore bound to be small ($`0.1`$ eV) when the reference system is an Al/$`Y`$ (100) junction with a density close to the average density of the Al/$`X`$ I and II junctions. We will thus neglect this correction, which leads to $`\mathrm{\Delta }V_1\mathrm{\Delta }V\left[Y/X(110)\right]`$, and hence to Eq. (12).

In Table 3, the average potential lineup at the Al/$`X`$ (100) I and II interfaces is compared to the predictions of the model, Eq. (12), obtained with $`Y=X`$ and with $`Y=\text{Ge}`$. The agreement between $`\overline{\mathrm{\Delta }V}^{\text{mod}}`$ \[$`\overline{\mathrm{\Delta }V}^{\text{mod}^{}}`$\] and the calculated $`\overline{\mathrm{\Delta }V}`$ is quite good, the discrepancy being 2% \[8%\] or less when the Al/$`X`$ (100) \[Al/Ge (100)\] junction is used as a reference system. Introducing the band energies in Eq. (12), we obtain Eq. (4) \[Eq. (5)\] with $`Y=X`$ \[$`Y=\text{Ge}`$\].


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# Superlight bipolarons and a checkerboard d-wave condensate in cuprates

## I Introduction: pairing is individual in many cuprates

Experimental mih ; cal ; tim ; guo ; shen2 ; ega ; mul2 ; she2  and theoretical phil ; alemot ; allen3 ; gor4 ; dev2  evidence for an exceptionally strong electron-phonon interaction in high temperature superconductors is now so overwhelming, that even some advocates of nonphononic mechanisms kiv  accept this fact. Our view is that the extension of the BCS theory towards the strong interaction between electrons and ion vibrations describes the phenomenon naturally. High temperature superconductivity exists in the crossover region of the electron-phonon interaction strength from the BCS-like to bipolaronic superconductivity as was predicted before ale0 , and explored in greater detail after the discovery alemot ; alej ; rice ; emi0 ; dev ; workshop ; micr .

Polarons form the Cooper pairs, if their coupling is not strong enough. However, real-space small bipolarons are also feasible due to a polaron collapse of the Fermi energy. There is strong evidence for the Bose-Einstein condensation of small bipolarons in many cuprates, in particular at low doping. Let us, for example, estimate a renormalised Fermi energy. The band structure is quasi-two-dimensional with a few degenerate hole pockets in cuprates. Applying the parabolic approximation for the band dispersion we obtain the renormalized Fermi energy as

$$ϵ_F=\frac{\pi n_id}{m_i^{}},$$
(1)
where $`d`$ is the interplane distance, and $`n_i,m_i^{}`$ are the density of holes and their effective mass in each of the hole subbands $`i`$ renormalized by the electron-phonon (and by any other) interaction. One can express the renormalized band-structure parameters through the in-plane magnetic-field penetration depth at $`T0`$, measured experimentally:

$$\lambda _H^2=4\pi e^2\underset{i}{}\frac{n_i}{m_i^{}}.$$
(2)
As a result, we obtain a parameter-free expression for the “true” Fermi energy as

$$ϵ_F=\frac{d}{4ge^2\lambda _H^2},$$
(3)
where $`g`$ is the degeneracy of the spectrum, which may depend on doping. One expects $`4`$ hole pockets inside the Brillouin zone (BZ) due to the Mott-Hubbard gap in underdoped cuprates. If the hole band minima are shifted with doping to BZ boundaries, all their wave vectors would belong to the stars with two or more prongs. The groups of wave vectors for these stars have only 1D representations. It means that the spectrum will be degenerate with respect to the number of prongs, i.e $`g2`$. Because Eq.(3) does not contain any other band-structure parameters, the estimate of $`ϵ_F`$ using this equation does not depend very much on the parabolic approximation for the band dispersion.

Generally, the ratios $`n/m^{}`$ in Eq.(1) and Eq.(2) are not necessarily the same. The ‘superfluid’ density in Eq.(2) might be different from the total density of delocalized carriers in Eq.(1). However, in a translationally invariant system they must be the same pop . This is also true even in the extreme case of a pure two-dimensional superfluid, where quantum fluctuations are important. One can, however, obtain a reduced value of the zero temperature superfluid density in the dirty limit, $`l\xi (0)`$, where $`\xi (0)`$ is the zero-temperature coherence length. The latter was measured directly in cuprates as the size of the vortex core. It is about 10 $`\AA `$ or even less. On the contrary, the mean free path was found surprisingly large at low temperatures, $`l`$ 100-1000 $`\AA `$. Hence, it is rather probable that novel superconductors are in the clean limit, $`l\xi (0)`$, so that the parameter-free expression for $`ϵ_F`$, Eq.(3), is perfectly applicable.

A parameter-free estimate of the Fermi energy obtained using Eq.(3) is presented in the Table.

The renormalised Fermi energy of about 30 cuprates is less than $`100`$ $`meV`$, in particular if the degeneracy $`g2`$ is taken into account. That should be compared with the characteristic phonon frequency, which is estimated as the plasma frequency of oxygen ions,

$$\omega _0=\sqrt{\frac{4\pi Z^2e^2N}{M}}.$$
(4)
One obtains $`\omega _0`$=$`84meV`$ with $`Z=2`$, $`N=6/V_{cell}`$, $`M=16`$ $`a.u.`$ for $`YBa_2Cu_3O_6`$. Here $`V_{cell}`$ is the volume of the (chemical) unit cell. The estimate agrees with the measured phonon spectra. As established experimentally in cuprates, the high-frequency phonons are strongly coupled with carriers. Therefore the low Fermi energy is a serious problem for the BCS (or Migdal-Eliashberg) approach. Since the Fermi energy is small and phonon frequencies are high, the Coulomb pseudopotential $`\mu _c^{}`$ is of the order of the bare Coulomb repulsion, $`\mu _c^{}\mu _c1`$ because the Tolmachev logarithm is ineffective. Hence, to get an experimental Tc, one has to have a strong coupling, $`\lambda >\mu _c`$. However, one cannot increase $`\lambda `$ without accounting for the polaron collapse of the band. Even in the region of the applicability of the Eliashberg theory (i.e. at $`\lambda 0.5`$), the non-crossing diagrams cannot be treated as vertex $`corrections`$, since they are comparable to the standard terms, if $`\omega _0/ϵ_F1`$. Because novel superconductors are in the nonadiabatic regime, interaction with phonons must be treated in the framework of the multi-polaron theory at any value of $`\lambda `$.

In many cases (Table) the renormalized Fermi energy is so small that pairing is certainly individual, i.e. the bipolaron radius is smaller than the inter-carrier distance. Indeed, this is the case, if

$$ϵ_F\pi \mathrm{\Delta }.$$
(5)
The bipolaron binding energy $`\mathrm{\Delta }`$ is thought to be twice the so-called pseudogap experimentally measured in the normal state of many cuprates, $`\mathrm{\Delta }100meV,`$ so that Eq.(5) is well satisfied in underdoped and even in a few optimally and overdoped cuprates. One should notice that the coherence length in the charged Bose gas has nothing to do with the size of the boson. It depends on the interparticle distance and the mean-free path, alemot , and might be as large as in the BCS superconductor. Hence, it is incorrect to apply the ratio of the coherence length to the inter-carrier distance as a criterium of the BCS-Bose liquid crossover. The correct criterium is given by Eq.(5).

## II Symmetry of the order parameter

The anomalous Bogoliubov average

$$F_{ss^{}}(𝐫_1,𝐫_2)=\mathrm{\Psi }_s(𝐫_1)\mathrm{\Psi }_s^{}(𝐫_2),$$

is the superconducting order parameter both in the weak and strong-coupling regimes ( $`\mathrm{\Psi }_s(𝐫)`$ annihilates a carrier with spin $`s`$ and coordinate $`𝐫`$ ). $`F_{ss^{}}(𝐫_1,𝐫_2)`$ depends on the relative coordinate $`\rho =𝐫_1𝐫_2`$ of two electrons of the pair, and on the center-of-mass coordinate $`𝐑=(𝐫_1+𝐫_2)/2`$. Hence, its Fourier transform, $`f(𝐤,𝐊)`$, depends on the relative momentum $`𝐤`$ and on the center-of-mass momentum $`𝐊.`$ In the BCS theory, where $`𝐊=0`$ (in a homogeneous superconductor), the Fourier transform of the order parameter is proportional to the gap in the quasiparticle excitation spectrum, $`f(𝐤,𝐊)\mathrm{\Delta }_𝐤`$. Hence the symmetry of the order parameter and the symmetry of the gap are the same in the weak-coupling regime. Under the rotation of the coordinate system, $`\mathrm{\Delta }_𝐤`$ changes its sign, if the Cooper pairing is d-wave. In this case the BCS quasiparticle spectrum is gapless.

In the bipolaron theory the symmetry of the Bose-Einstein condensate is not necessarily the same as the “internal” symmetry of a pair alesym . While the latter describes transformation of $`f(𝐤,𝐊)`$ with respect to the rotation of $`𝐤`$, the former (“external”) symmetry is related to the rotation of $`𝐊.`$ Therefore it depends on the bipolaron band dispersion, but not on the symmetry of the bound state.

As an example, let us consider a tight-binding bipolaron spectrum comprising two bands on a square lattice with the period $`a=1,`$

$`E_𝐊^x`$ $`=`$ $`t\mathrm{cos}(K_x)t^{}\mathrm{cos}(K_y),`$ (6)
$`E_𝐊^y`$ $`=`$ $`t^{}\mathrm{cos}(K_x)+t\mathrm{cos}(K_y).`$
They transform into one another under $`\pi /2`$ rotation. If $`t,t^{}>0,`$$`x\mathrm{"}`$ bipolaron band has its minima at $`𝐊=(\pm \pi ,0)`$ and $`y`$-band at $`𝐊=(0,\pm \pi )`$. These four states are degenerate, so that the condensate wave function $`\psi _s(𝐦)`$ in the site space, $`𝐦=(m_x,m_y),`$ is given by

$$\psi _s(𝐦)=N^{1/2}\underset{𝐊=(\pm \pi ,0),(0,\pm \pi )}{}b_𝐊e^{i𝐊𝐦}.$$
(7)
where $`b_𝐊=\pm \sqrt{n_s}`$ are $`c`$-numbers at $`T=0.`$ The superposition, Eq.(7), respects the time-reversal and parity symmetries, if

$$\psi _s^\pm (𝐦)=\sqrt{n_s}\left[\mathrm{cos}(\pi m_x)\pm \mathrm{cos}(\pi m_y)\right].$$
(8)
Two order parameters, Eq.(8), are physically identical because they are related by the translation transformation, $`\psi _s^+(m_x,m_y)=\psi _s^{}(m_x,m_y+1)`$. Both have a $`d`$-wave symmetry changing sign, when the lattice is rotated by $`\pi /2`$, Fig.1. The $`d`$-wave symmetry is entirely due to the bipolaron energy dispersion with four minima at $`𝐊\mathrm{𝟎}`$. When the bipolaron spectrum is not degenerate and its minimum is located at $`\mathrm{\Gamma }`$ point of the Brillouin zone, the condensate wave function is $`s`$-wave with respect to the center-of-mass coordinate. The symmetry of the normal state (pseudo)gap has little to do with the symmetry of the order parameter in the strong-coupling regime. The one-particle pseudogap is half of the bipolaron binding energy $`\mathrm{\Delta }/2`$, and does not depend on any momentum in zero order of the polaron bandwidth, i.e. it has an “$`s\mathrm{"}`$-wave symmetry. In fact, due to a finite dispersion of polaron and bipolaron bands, the pseudogap is an $`anysotropic`$ s-wave. A multi-band electron structure can include bands weakly coupled with phonons which could overlap with the bipolaronic band. In this case CBG coexists with the Fermi gas, like $`{}_{}{}^{4}He`$ bosons coexist with $`{}_{}{}^{3}He`$ fermions in the mixture of Helium-4 and Helium-3 alemot . The normal state one-particle excitation spectrum of such mixtures is gapless.

## III Checkerboard modulations of the superconducting gap

Independent observations of normal state pseudogaps in a number of magnetic and kinetic measurements, and unusual critical phenomena tell us that many cuprates may not be $`BCS`$ superconductors. Indeed their superconducting state is as anomalous as the normal one. In particular, there is strong evidence for a $`d`$-like order parameter (changing sign when the $`CuO_2`$ plane is rotated by $`\pi /2`$) in cuprates ann . A number of phase-sensitive experiments pha  provide unambiguous evidence in this direction; furthermore, the low temperature magnetic penetration depth bonn ; xia  was found to be linear in a few cuprates as expected for a d-wave BCS superconductor. However, different tunnelling spectroscopies, in particular $`c`$-axis Josefson tunnelling klem , and some high-precision magnetic measurements mulsym  show a more usual $`s`$-like symmetry. Other studies even reveal an upturn in the temperature dependence of the penetration depth below some characteristic temperature wal . Also both angle-resolved photoemission (ARPES) and tunnelling spectroscopies often show a very large energy gap with $`2\mathrm{\Delta }/T_c`$ ratio well above that expected in any-coupling BCS theory.

Strong deviations from the Fermi/BCS-liquid behaviour are suggestive of a new electronic state in cuprates, which could be a charged Bose liquid of bipolarons. In the bipolaron theory the symmetry of the Bose-Einstein condensate on a lattice should be distinguished from the ‘internal’ symmetry of a single-bipolaron wave function, and from the symmetry of a single-particle excitation gap. As described above the Bose-Eistein condensate of bipolarons could be $`d`$-wave, if bipolaron bands have their minima at finite $`𝐊`$ in the center-of-mass Brillouin zone. At the same time the single-particle excitation spectrum is an anysotropic $`s`$-wave providing a possible explanation of conflicting experimental observations.

The two-dimensional patterns, Fig.1, are oriented along the diagonals, i.e. the $`d`$-wave bipolaron condensate is ‘striped’. Hence there is a fundamental connection between stripes detected by different techniques tran ; bia  in cuprates and the symmetry of the order parameter alesym . Originally antiferromagnetic interactions were thought to give rise to spin and charge segregation (stripes) zaa . However the role of long-range Coulomb and Fröhlich interactions was not properly addressed. We showed that the Fröhlich electron-phonon interaction combined with the direct Coulomb repulsion does not lead to charge segregation like strings or stripes in doped insulators, and the antiferromagnetic exchange interaction is not sufficient to produce long stripes either alekabstr .

If (bi)polaronic carriers in many cuprates are in a liquid state, one can pose a key question of how one can see stripes at all. Actually, the bipolaron condensate is striped owing to the bipolaron energy band dispersion, as discussed above. In this scenario the hole density, which is about twice of the condensate density at low temperatures, is striped, with the characteristic period of stripes determined by inverse wave vectors corresponding to bipolaron band-minima. Such interpretation of stripes is consistent with the inelastic neutron scattering in $`YBa_2Cu_3O_{7\delta }`$ , where the incommensurate peaks were observed $`only`$ in the $`superconducting`$ state bou . The vanishing at $`T_c`$ of the incommensurate peaks is inconsistent with any other stripe picture, where a characteristic distance needs to be observed in the normal state as well. On the contrary, with the d-wave $`striped`$ Bose-Einstein condensate the incommensurate neutron peaks should disappear above $`T_c`$, as observed. Also recent X-ray spectroscopy boz  did not find any bulk charge segregation in the normal state of a high-$`Tc`$ $`LaCuO_{4+\delta }`$ suggesting an absence of in-plane carrier density modulations in this material above $`T_c`$.

The $`d`$-wave condensate reveals itself as a checkerboard real-space modulation of the hole density, Fig.1. Then the superconducting gap should be modulated as well. Indeed, as shown in Ref.aleand , the single-particle excitation spectrum of the bipolaronic superconductor can be obtained using the BCS excitation spectrum but with a negative chemical potential,

$$ϵ(𝐤)=\left[(k^2/2m^{}+\mathrm{\Delta }_p)^2+\mathrm{\Delta }_c(T)^2\right]^{1/2},$$
(9)
where $`\mathrm{\Delta }_c(T)^2=constant\times |\psi _s|^2`$ is a coherent component of the gap. This spectrum is quite different from the BCS quasiparticles because the chemical potential is negative with respect to the bottom of the single-particle band, $`\mu =\mathrm{\Delta }_p`$. A single particle gap, $`\mathrm{\Delta }/2`$, defined as the minimum of $`ϵ(𝐤)`$, is given by

$$\mathrm{\Delta }/2=\left[\mathrm{\Delta }_p^2+\mathrm{\Delta }_c(T)^2\right]^{1/2}.$$
(10)
It varies with temperature from $`\mathrm{\Delta }(0)/2=\left[\mathrm{\Delta }_p^2+\mathrm{\Delta }_c(0)^2\right]^{1/2}`$ at zero temperature down to the temperature independent $`\mathrm{\Delta }_p`$ above $`T_c`$. The spectrum, Eq.(10) was obtained for a homogeneous condensate. However, in the framework of a semiclassical approximation, we can apply Eq.(10) also with a modulated $`\psi _s(𝐦)`$, if the period of modulations is large enough alekab . As a result, the superconducting gap is modulated. Importantly, the checkerboard modulation of the gap have been observed in the tunnelling experiments with hoff  and without kapit ; hoff2  applied magnetic field in $`Bi`$ cuprates.

In conclusion, I have shown that there is a real-space pairing in many cuprates due to the polaron collapse of the Fermi energy. Remarkably, the bipolaron theory provides an explanation of the d-wave order parameter, the anysotropic s-wave single-particle gap, and its stripe checkerboard modulations below $`T_c`$ within a single microscopic approach.

This work has been supported by the Leverhulme Trust (grant F/00261/H). I greatly appreciate enlightening discussions with I. Bozovic, K. McElroy, V. V. Kabanov, A. J. Leggett, D. Mihailovic, and K. A. Müller.