text:
# Strong Gravitational Lensing and the Structure of Quasar Outflows

## 1. Introduction

The standard model for quasars consists of a central continuum emitting region (possibly an accretion disk), broad and narrow line regions (BLR and NLR respectively), and a torus. Among these components only the NLR can be resolved in nearby quasars to reveal a stratified structure and a cone-shape geometry. The physical nature of the other components is subject to an ongoing debate, e.g., it is not known whether the BLR is in the form of virialized clouds (e.g., Kaspi & Netzer 1999) or a continuously outflowing wind (e.g., Murray, Chiang, Grossman, & Voit 1995; hereafter MCGV).

Observations indicate that outflowing gas is a common phenomenon in quasars. Such gas is intrinsic to the quasar, as has been shown for the high velocity ($`10^3\mathrm{km}\mathrm{s}^1`$), broad absorption line (BAL) flows in BALQSOs (Weymann 1977). The quasar unification scheme (e.g., Elvis 2000) suggests that BAL flows are ubiquitous and their detection (in some $`15\%`$ of type-I objects; Hewett & Foltz 2003) requires a fortuitous line of sight to the central engine.

There have been several unsuccessful attempts to constrain the location of BAL flows via the detection of variations in velocity or ionization. de Kool et al. (2001) have detected absorption from excited levels of iron which allowed location estimates in a subclass of BALQSOs (FeLoBALQSOs). An indirect measure of the gas location relies on the observationally motivated assumption that it is accelerated by radiation pressure force (Arav 1996). This has been the focus of many works concerning the dynamical modeling of such flows.

Dynamical models consist of cloud (e.g., Chelouche & Netzer 2001, hereafter CN01), wind (MCGV, Proga, Stone, & Kallman 2000; hereafter PSK), and cloud-wind models (e.g., Arav, Li, & Begelman 1994; hereafter ALB). Some versions of such models can be brought to some agreement with observations. They do not however agree among themselves concerning the mass flow rate and other important parameters. Thus, despite some 30 years of research, several key properties of BAL flows remain unknown.

In this Letter we show that strong lensing can add invaluable information on the structure of BAL flows: In §2 we define our sample of lensed BALQSOs. §3 discusses the observational constraints on several flow models. Future prospects and caveats are discussed in §4. Summary follows in §5.

## 2. Lensed BALQSOs: Geometry and Sample

In gravitationally lensed systems, each image corresponds to a different line of sight to the central object. For typical lens configurations (figure 1), the angle between the line of sights, $`\mathrm{\Delta }\phi `$, is of order of the separation angle between the images ($`\mathrm{\Delta }\theta `$; see e.g., Schneider, Ehlers, & Falco 2000).

We consider 7 lensed and one lens candidate (UM 425; see however Aldcroft & Green 2003 who favour a binary quasar interpretation for this system) BALQSOs whose properties were taken from CASTLES111http://cfa-www.harvard.edu/castles/ (Muñoz et al. 1998) and Michalitsianos et al. (1997), and are given in table 1. Assuming a typical type-I quasar continuum with $`\alpha _{ox}=1.4`$ (Green et al. 1995) and a X-ray (0.1-10 keV) continuum slope, $`\alpha _x=0.9`$, the mean demagnified bolometric luminosity of the quasars in our sample is $`10^{46}\mathrm{erg}\mathrm{s}^1`$ (Chartas 2000; this value depends on the assumed lens model and is somewhat insecure for double imaged lenses).

Spectroscopic observations show that in most lensed BALQSOs, the absorption troughs are similar between different images to within S/N and resolution limits. This is probably not a selection effect (due to the search criteria used for finding lensed objects) since the fraction of BALQSOs among lensed quasars is larger (Chartas 2000; or similar but not smaller) than their fraction among quasars (Hewett & Foltz 2003). This means that BAL flows are relatively isotropic on small angular scales. Nevertheless, for two objects in our sample (APM 08279+5255 and the lens candidate UM 425) there seem to be noticeable differences in the BAL troughs between the images. We discuss the implications of these results on various dynamical models in §3.

## 3. Implications for quasar outflow models

Here we show that by comparing BAL features of different images one can put constraints on existing flow models. This results from the different characteristic angular scale of the flow predicted by different models. Below we discuss each class of models separately.

### 3.1. Single cloud models

This model was initially invoked to explain the BLR gas and only later applied to BAL flows. Several works (e.g., Blumenthal & Mathews 1979, hereafter BM79) have demonstrated a qualitative agreement between model and observations in terms of the flow velocity and spectral features.

In these models the clouds are spherical to a good approximation (BM79) and are confined by some external pressure, $`P`$ ($`Pr^2`$ is typically assumed where $`r`$ is the distance from the central object; ALB). The clouds are photoionized by the quasar radiation field and their ionization structure depends primarily on the ionization parameter, $`U_x`$ (defined as the ratio of photon density in the range 0.1-10 keV to gas number density; CN01). The terminal velocity of the cloud ($`v_{10000}`$; in units of $`10^4\mathrm{km}\mathrm{s}^1`$) is given by

$$v_{10000}0.1L_{45}^{1/2}r_{17}^{1/2}M^{1/2},$$
(1)
where $`r_{17}=r/10^{17}`$ cm is the launching distance, $`L_{45}`$ the bolometric luminosity in units of $`10^{45}\mathrm{erg}\mathrm{s}^1`$, and $`M`$ the “force multiplier” (the ratio of the total to the Compton radiation pressure force; $`M(r)=`$ const. for the assumed pressure profile; CN01). For $`10^5<U_x<0.1`$ and the typical velocities and column densities of BAL flows, $`M`$ can be approximated up to a factor $`3`$ by

$$M0.3ZU_x^1,$$
(2)
where $`Z`$ is the gas metalicity normalized to solar values.

High S/N spectroscopy combined with detailed photoionization calculations can constrain the ionization parameter, $`U_x`$ and the column density $`N_{21}`$ (in units of $`10^{21}\mathrm{cm}^2`$; assuming $`Z=1`$) of the outflowing gas. These seem to cluster around $`U_x10^4,N_{21}1`$ for BAL flows (Arav et al. 2001) and $`U_x10^5,N_{21}1`$ for FeLoBAL flows (de Kool et al. 2002). Therefore, high ionization BAL flows that are launched from the centers ($`r_{17}50`$) of luminous quasars ($`L_{45}=10`$) would reach a terminal velocity $`15,000\mathrm{km}\mathrm{s}^1`$ (equations 1 & 2) which is in qualitative agreement with observations.

Combining equations 1 & 2 we obtain,

$$r_{17}3\times 10^3v_{10000}^2L_{45}ZU_x^1,$$
(3)
where $`v_{10000}`$ is inferred from the blue wing of BAL troughs. This estimate for $`r_{17}`$ can be compared to those derived for FeLoBALQSOs: For FBQS 1044+3656 ($`L_{45}=10v_{10000}0.5`$) de Kool et al. (2002) conclude that $`r_{17}2\times 10^4`$ (see however Everett, Königl, & Arav 2002) which is consistent with the dynamical estimate for this object ($`r_{17}10^4`$).

TABLE 1

Properties of the Lensed BALQSOs Sample     Object $`z_s`$ $`z_l`$ $`\mathrm{\Delta }\theta `$ $`t_{\mathrm{lag}}`$ $`v_{10000}`$ Refs.  $`\left[1\right]`$          APM 08279+5255 3.91  0.38” - 1 a,b  SBS 1520+530 1.86 0.72 1.56” 130 2 c,d  HE 2149-2745 2.03 0.49 1.7” 103 0.8 c,e  RX J 0911.4+0551 2.8 0.77 0.48” 146 0.3 c,e  PG 1115+080 1.72 0.37 2.3” 25 0.6 c,f  UM 425 1.46 0.6 6.5” - 1.2 g,h,i  H 1413+117 2.55  1.35” - 0.9 c,j  J 1004+1229 2.66 0.95 1.54” - 1 k     The sample of lensed (and the lens candidate UM 425) BALQSOs:  Object’s name,  Source redshift,  Lens redshift,  Image separation (arcseconds),  Time lag between images (days),  Maximum flow velocity ($`10000\mathrm{km}\mathrm{s}^1`$) inferred from the absorption line troughs,  References: (a) Chartas et al. 2002, (b) Irwin et al. (1998), (c) Chartas (2000), (d) Burud et al. (2002), (e) Bade et al. (1997), (f) Michalitsianos et al. 1996, (g) Michalitsianos et al. 1997, (h) Green et al. (2001), (i) Aldcroft & Green (2003) ,(j) Hutsemekers (1993), (k) Lacy et al. (2002) .

It follows from the definition of $`U_x`$ that the angle subtended by a spherical cloud with a column density $`Z^1N_{21}`$ (e.g., Arav et al. 2001) is

$$\mathrm{\Delta }\phi _c10U_xr_{17}L_{45}^1Z^1N_{21}\mathrm{arcseconds}.$$
(4)
By combining equations 3 and 4 we obtain

$$\mathrm{\Delta }\phi _c3\times 10^2v_{10000}^2N_{21}\mathrm{arcseconds}.$$
(5)
Thus, for all objects in our sample the cloud’s lateral size, $`10^{11}r_{17}\mathrm{\Delta }\phi _c\mathrm{cm}`$, is smaller than the Schwartzschild radius ($`R_s`$) of the central black hole (BH; using the luminosity–BH mass relation of Kaspi et al. 2000). The fact that BAL flows only partially cover the ionizing source (whose size is $`10R_s`$ for a standard accretion disk; Arav et al. 2001) corroborates our size estimates.

Inspection of table 1 reveals that for all objects, $`\mathrm{\Delta }\phi _c\mathrm{\Delta }\theta `$. For clouds to show identical absorption features in all quasar images, their aspect (lateral to radial) ratio should reach $`10^3`$ for the more extreme cases in our sample (the cloud model is however consistent with the different BAL troughs in e.g., UM 425; Aldcroft & Green 2003). Such oblate clouds would probably be destroyed over dynamical timescales and a coherent acceleration is therefore unlikely (BM79).

Thus far, we have considered single clouds. Nevertheless, the flow column density may be distributed among many clouds (this is likely given the smooth nature of BAL troughs). For simplicity we assume that the flow consists of $`n`$ identical clouds, each with a column $`Z^1N_{21}/n`$. In this case, $`\mathrm{\Delta }\phi _c`$ is reduced by a factor $`n`$. This model is sometimes referred to as the tube model where the aspect ratio of the flow is much smaller than unity (contrary to what is implied by lensed quasar observations). The probability for a perfect alignment of the tube to several lines of sight is negligibly small . Thus, more likely geometries are those of a sheet or a cone which are naturally accounted for by wind models.

### 3.2. Clumpy wind models

In this model (ALB), the flow is assumed to consist of numerous small clouds (“cloudlets”). Isotropy is assumed in the statistical sense, i.e., each line of sight corresponds to a different realization of the same cloud distribution. Thus, each image of the quasar may show different absorption features due to statistical fluctuations in the number of clouds between different lines of sight which follow the Poissonian distribution. Following ALB, we assume identical cloudlets. Denoting the total optical depth by $`\tau `$ and the fluctuations in the optical depth by $`\mathrm{\Delta }\tau `$, one can estimate (assuming 1$`\sigma `$ fluctuations) the average number of clouds along the lines of sight,

$$n\tau ^2\mathrm{\Delta }\tau ^2$$
(6)
for $`\mathrm{\Delta }\tau <\tau `$. As the spectral signature of a single cloud cannot extend considerably beyond one thermal width in velocity space (typically $`10\mathrm{km}\mathrm{s}^1`$) it allows us to constrain, or put lower limits to the number of clouds in each velocity bin for non-saturated troughs. In most cases, BAL profiles of different images are identical within S/N limits implying that the number of clouds in each velocity bin is $`1`$ and their total number $`100`$. This information is orthogonal to that concerning the filling factor of flows. Furthermore, observing systematic differences over a wide velocity range would indicate changes in the global flow properties (in the cloud distribution function). Such variations seem to be implied by the dissimilarities in BAL troughs for two objects in our sample (APM 08279+5255 and UM 425; see §4.1) although higher quality data are needed to confirm this point.

### 3.3. Continuous wind models

Time independent continuous wind models usually assume gas which expands according to the spherical continuity condition $`\rho \mathrm{\Omega }r^2v^1`$ ($`\rho ,v`$ being the gas density and velocity respectively, and $`\mathrm{\Omega }`$ the opening angle; e.g., MCGV). This assumption is justified for $`\mathrm{\Omega }4\pi `$. However, flows are likely to evaporate quickly through their rims for considerably smaller $`\mathrm{\Omega }`$, since the expansion timescale ($`\sqrt{\mathrm{\Omega }}r_{17}/v_s`$, $`v_s20\mathrm{km}\mathrm{s}^1`$ is the sound speed) is smaller than the dynamical timescale ($`r_{17}/v_{10000}`$). Put differently, for $`\sqrt{\mathrm{\Omega }/4\pi }400v_{10000}^1`$ arcseconds, the gas would evaporate before reaching its terminal velocity. Therefore, a confining pressure must be invoked, and it is highly unlikely that the resulting continuity condition would mimic a spherical expansion. If the differences in BAL troughs in APM 08279+5255 and UM 425 are real, these imply that $`\sqrt{\mathrm{\Omega }/4\pi }\mathrm{\Delta }\theta `$ (otherwise the probability for detecting such differences would be negligible). Thus, at least for these objects (see also Chelouche & Netzer 2003), the assumption of spherically expanding flows is unwarranted and alternative geometries with very different spectral predictions are more appropriate \[e.g., confined (Königl & Kartje 1994) and freely expanding flows (Chelouche 2003)\].

### 3.4. Time dependent wind models

Time-dependent calculations (PSK) show that Rayleigh-Taylor, Kelvin-Helmholtz, and radiative instabilities result in a filamentary sub-structure of the flow. Currently, there are no spectral predictions for their model and direct comparison with observations is complicated. Nevertheless, the results for the angular distribution of $`U_x`$ and density (see figure 4a,b in PSK for the angular range subtended by high velocity gas) imply that the extreme ($`>10`$ orders of magnitude!) variations over $`10\mathrm{°}`$ result from opacity rather than density effects. Thus, $`U_x`$ is a measure of the transmitted spectrum. Assuming that $`U_x`$ is a continuous function of angle down to small scales, then interpolation of PSK results predicts it should differ by many orders of magnitude over $``$1 arcsecond scales. Such extreme variations would result in different spectral signatures between quasar images which are not observed. A more detailed study of this effect (e.g., by accounting for the finite size of the continuum source and the stratified flow structure) is limited by the low resolution of current simulations. This apparent contradiction between model and observations may be resolved if there is a typical scale (larger than $`r\mathrm{\Delta }\theta 10^{14}`$cm) below which variations are suppressed (e.g., due to the dissipation of turbulence below some scale or by the stablizing effect of magnetic fields; e.g., Proga 2003).

## 4. Future prospects

We have demonstrated a new method for investigating the structure of BAL flows. Similar reasoning can be applied to additional types of flows namely, narrow absorption line (NAL) and X-ray BAL (XBAL) flows. For NAL flows $`N_{21}2`$ (e.g., Kraemer et al. 2002; but see also Hamann, Netzer, & Shields 2000 for lower values) and $`v_{10000}0.1`$ (Crenshaw et al. 1999) and, therefore, $`\mathrm{\Delta }\phi _c2`$ arcseconds, i.e., the single cloud model cannot be firmly ruled out for typical lens separations. This stems from the fact that such gas lies at larger distances and is more dilute. XBALs have so far been observed in two objects (APM 08279+5155 and PG 1115+080; Chartas et al. 2002, 2003) and seem to have $`N_{21}=10^2`$, and $`v_{10000}=10`$. This gives $`\mathrm{\Delta }\phi _c10^2`$ arcsecond. Nevertheless, due to the complications associated with X-ray spectroscopy, it is difficult to compare XBALs of different images.

Given several lines of sight, it may be possible to detect whether the flow is collimated and at what direction. From pure geometrical considerations, a collimated flow will show a velocity difference $`\delta vv\delta \phi `$ between two lines of sight $`\delta \phi `$ apart. For SBS 1520+530, $`\delta v0.1\mathrm{km}\mathrm{s}^1`$, i.e., within the resolution of next generation spectrometers. This, combined with an independent measure for the orientation of the quasar (e.g., via the detection of a jet), may allow us to ascertain whether BAL flows are predominantly polar or planar and how they relate to other components of the quasar.

Outflows are likely to rotate around the central object (e.g., MCGV) and it may be possible to detect spectral absorption features sweeping across our line of sight over Keplerian timescales,

$$\tau _{\mathrm{Kep}.}10^6v_{10000}^3L_{45}Z^{3/2}U_x^{3/2}\mathrm{\Gamma }^{1/2}\mathrm{\Delta }\phi \mathrm{days},$$
(7)
($`\mathrm{\Gamma }`$ is the luminosity in units of the Eddington luminosity). Typically $`\tau _{\mathrm{Kep}.}100`$ days for BAL flows in quasars with $`\mathrm{\Gamma }=0.1`$. Detecting such events would set more stringent limits on the geometry of the outflowing gas and may reveal the angular momentum balance in the inner quasar regions (perhaps even in the accretion disk). Such studies may also provide better estimates for $`H_0`$ since absorption events do not depend on the global geometry of the system and are less smeared in time compared to emission events.

### 4.1. Caveats

We have assumed that flow properties do not change on timescales shorter than the time lag, $`t_{\mathrm{lag}}`$, between quasar images. This requires that both the dynamical timescale, $`t_{\mathrm{dyn}}`$ and the intrinsic flux variability timescale, $`t_{\mathrm{flux}}`$, are longer than $`t_{\mathrm{lag}}`$. Indeed, the dynamical timescale, $`t_{\mathrm{dyn}}v_{10000}^3L_{45}ZU_x^1`$ days is much longer than $`t_{\mathrm{lag}}`$ (table 1) for UV flows ($`t_{\mathrm{dyn}}t_{\mathrm{lag}}`$ for XBALs) and recent variability studies of high redshift quasars indicate that $`t_{\mathrm{flux}}t_{\mathrm{lag}}`$ (Kaspi et al. 2003). Thus, any differences between UV BAL troughs are probably not related to time-lag effects.

An additional complication arises from micro-lensing (ML) by stars in the lensing galaxy which can differentially (de-)magnify the continuum emitting region (e.g., Wambsganss 1992). Its effect, being line of sight dependent (e.g., Ofek & Maoz 2003), may alter the shape of non-black troughs and result in apparent discrepancies between them. A more quantitative discussion requires further study (Chelouche 2003, in preparation) and is beyond the scope of this Letter.

## 5. Conclusions and Summary

In this Letter we show that by analyzing the spectral absorption features of spatially resolved lensed BALQSOs, one can obtain invaluable information concerning the geometry and sub-structure of BAL flows. Given the currently available spectroscopic data we conclude that such flows are relatively isotropic on a few arcsecond scales. Our analysis suggests that the coherently accelerated cloud model (and the related tube model) are inconsistent with observations, and that BAL flows are probably made of one or several outflowing sheets or cones with lateral dimensions much larger than the typical separation between quasar images. The similarity of the absorption features between different images is inconsistent with naive interpretations of time-dependent dynamical simulations. This may indicate a typical length scale below which sub-structure is suppressed. Future high resolution spectroscopy of lensed BALQSOs may reveal whether such flows are collimated and distinguish between polar and planar flow configurations. Multi-epoch observations may put further constraints on the lateral geometry and dynamics of BAL flows as well as lead to better estimates for $`H_0`$. Such information cannot be obtained from observations of non-lensed BALQSOs, and is imperative to our understanding of quasar structure and the physical processes near black-holes.

The author wishes to thank H. Netzer, I. Goldman, O. Shemmer, and E. O. Ofek for many helpful discussions, and the anonymous referee for his valuable comments. The Dan David Prize scholarship is gratefully acknowledged.


format: text

text:
# Self-organized current transport through low angle grain boundaries in YBa2Cu3O7-δ thin films, studied magnetometrically

## I INTRODUCTION

High temperature superconductors characteristically have highly anisotropic properties and a short scale of the superconducting coherence length $`\xi `$. As a consequence, the critical current density across grain boundaries can be significantly reduced relative to that which flows within grains. For reasons that are not well understood, a large misalignment of adjacent grains suppresses the order parameter along the grain boundary (GB) and as a result, the adjacent grains are weakly linked. The weak-link behavior of a high-angle grain boundary and a near-exponential decrease in the GB critical current density $`J_c^{GB}`$ with misorientation angle were first studied by Dimos et al. Dimos88  in YBa2Cu3O7-δ materials. Since then, a number of studies have been conducted on this and other high-$`T_c`$ superconductors, as reviewed recently by Hilgenkamp and Mannhart.HM-RMP02  This review article provides an excellent overview of grain boundaries in these materials, the controlled synthesis of GBs, current transport, and related topics. Much earlier work focussed on the properties of GBs with relatively large misorientation angles $`\theta >`$ 10, where intergrain current conduction is severely suppressed. The present work concentrates on materials with lower angle GBs, which are contained in YBCO rings for magnetometric study.

The regime of lower angle grain boundaries is interesting, for with decreasing tilt angle $`\theta `$, the mode of current conduction appears to cross-over from weak to strong linkage. Technologically this is highly relevant: recently developed methods for forming highly-textured coated conductors, such as rolling-assisted biaxially textured substrates (RABiTS)Goyal96 ; Goyal99  and ion-beam assisted deposition (IBAD)Iijima92 ; Reade93 ; Wu95 , vastly improve the current conduction in multicrystalline coated conductors of high-temperature superconductors, by reducing the average misorientation into a regime of low angles $`\theta 7^{}`$. For sufficiently small angles, the material between dislocation cores on the grain boundary is only mildly perturbed and this provides a strong conduction channel comparable to or wider than the in-plane coherence length.Verebelyi00  For further development of coated conductors, an understanding of low-angle GBs is important, for it gives guidance as to how highly textured the materials must be. Specifically, are low-angle GBs still weak-linked and responsible for large reductions of the GB current density? How does the application of an external magnetic field affect the current flow?

This magnetometric study of low-angle GBs is based on a simple equation from electrodynamics. A circulating current generates a magnetic dipole moment according to the equation

$$m=(1/2c)(𝒓\times 𝑱(𝒓))\text{d}V$$
(1)
where $`𝑱`$ is the current density at location $`𝒓`$. This expression tells us that once the current configuration is established, the current or (spatially uniform) current density can be calculated from the measured magnetic moment of a sample. The current configuration is related to the sample geometry. With the sensitivity of SQUID-based instrumentation and a simple ring geometry that helps define the current path,Jung93 ; Darhmaoui96 ; Charalambous98 ; Claus01  we obtain the critical current density $`J_c`$ flowing through grain boundaries in the high-temperature superconductor YBa2Cu3O7-δ (YBCO), and for comparison, the $`J_c`$ of companion rings with no GBs. Furthermore, the magnetic responses $`m(H)`$ of the rings are compared and contrasted. We observe a large peak in the decreasing field branch of the $`m(H)`$ curves for GB rings with $`\theta `$ = 5.1 and 7 and show that its appearance arises largely from a cancellation of the applied magnetic field by self field effects on weakly linked grain boundaries.

## II MAGNETIC MOMENTS in the CRITICAL STATE

In the critical state model, one assumes that critical currents with density $`\pm J_c`$ flow throughout the superconductor. In this work, the currents are induced by applying a large magnetic field $`H_{app}`$ perpendicular to flat, planar samples. It is then straightforward to integrate Eq. 1 and obtain the associated magnetic moment $`m`$ for several of the sample geometries used here. For example, a flat strip of thickness $`d`$, length $`\mathrm{}`$, and width $`w`$ has

$$m_{strip}=J_cd\mathrm{}w^2/40\times [1w/3\mathrm{}]$$
(2)
according to the sandpile model.Gyorgy  This and following expressions have cgs units with dimensions in cm, $`J`$ in A/cm2, and $`m`$ in erg/G = emu. For the long narrow strips considered here, the factor $`[1w/3\mathrm{}]1`$ will be neglected. Equation 2 also gives the moment of an “open circuit” thin ring of the same thickness and width, where $`\mathrm{}=2\pi R`$ for a ring of radius $`R`$.

$$m_{openring}=J_cd(2\pi R)w^2/40$$
(3)
Another standard case is that of a disk of outer radius $`a`$ and thickness $`d`$. Here one has

$$m_{disk}=J_c\pi da^3/30$$
(4)
From this, it follows that a continuous ring with outer radius $`a`$ and inner radius $`a_1`$ has moment

$$m_{ring}=J_c\pi d(a^3a_1^3)/30$$
(5)
For a thin ring with $`aa_1=w<<a`$, Eq. 5 is nearly the same as the simplest expression

$$m_{loop}=I_c\pi a^2/c$$
(6)
where $`I_c`$ is the critical current and the speed of light $`c`$ has value 10 in these laboratory units.

Let us now consider the case of a thin ring that crosses a grain boundary (GB). The GB is expected to have a lower critical current density $`J_c^{GB}`$ and lower critical current $`I_c^{GB}`$ than the surrounding epitaxial YBCO grain film with critical current density $`J_c^{Gr}`$. When applying a magnetic field, we first induce currents that circulate around the outer and inner circumferences of the ring and that screen flux from the central hole;Brandt97  simultaneously flux penetrates into the grain YBCO and more deeply into the GB. When the current exceeds $`I_c^{GB}`$, flux enters the hole along the GB and is trapped there. Application of still higher fields drives flux into all of the grain material where currents with density $`J_c^{Gr}`$ flow throughout. Thus a portion of the current approaching a GB can cross it and generate the magnetic moment of a loop, Eq. 6. The self-organizing, remaining portion of the current makes a “U-turn,”Polyanskii96  giving the magnetic moment of a strip, Eq. 2. The resulting Bean-like flux profile is displaced from the center of the strip, just like the case of a superconducting strip carrying both a transport current and critical state currents. Let us define $`\mathrm{\Delta }`$ by $`J_c^{GB}=(\mathrm{\Delta }/w)J_c^{Gr}`$ as a measure of the GB current (geometrically $`\mathrm{\Delta }/2`$ corresponds to the displacement of the flux profile from the center-line of the ’strip’). Then we have

$$m_{GBring}=m_{loop}+m_{strip}$$
(7)
$$m_{GBring}=(\mathrm{\Delta }/w)J_c^{Gr}wd\pi a^2/c+J_c^{Gr}d(2\pi a)(w\mathrm{\Delta })^2/40$$
(8)
These expressions ignore terms of order $`(w/a)^2`$. Experimentally, we determine $`J_c^{Gr}`$ in a separate experiment, then solve Eq. 8 for $`(\mathrm{\Delta }/w)`$, from which $`J_c^{GB}`$ is obtained.

## III EXPERIMENTAL ASPECTS

In order to use the above equations effectively for this study, samples were specially designed as rings in the following process. Films of YBCO were prepared on SrTiO3 (STO) -tilt bicrystal substrates by pulsed laser deposition. Three ring samples were made from each YBCO film using standard optical photolithography techniques. One ring was placed across a grain boundary so as to contain two grain boundaries (GB ring); two other rings were patterned on each of the two adjoining single crystals (grain rings). All three rings have the same geometry with an outside diameter $`2a`$ of 3 mm, an inside diameter $`2a_1`$ of 2.8 mm giving a ring width $`w`$ of 0.10 mm, and a thickness $`d`$ of 200 nm. The substrate was cut into three pieces, each containing just one ring. Note that all three rings come from a single YBCO film and as a result, the films *per se* should have the same properties, such as current density, pinning force, etc. Bicrystal substrates with 1.8, 2.8, 5.1 (two samples), and 7 -tilt boundaries were used to make GB and companion grain ring samples. Sometimes the current density can be diminished by external degrading factors, such as cracks on a sample or by maltreatment. To cross-check the deduced current density values of grain rings, some grain rings were made into an open circuit by etching a line across the 100 $`\mu `$m width (open rings). This changes the geometry of the current path without changing the properties of the superconductor; consistent values of $`J_c`$ were obtained.

Magnetic measurements were conducted with a SQUID-based Quantum Design MPMS-7 magnetometer. An individual sample was mounted on a Si disk with Duco cement and placed in a Mylar tube for support. For each ring, the magnetic moment was measured as a function of temperature and magnetic field. For temperature sweep experiments, a magnetic field was applied parallel to the c-axes of YBCO film at 5 K (500 Oe, 3 kOe, and 3 kOe for grain, GB, and open rings, respectively); the field levels were chosen to ensure each sample geometry was fully penetrated by the field. Subsequently the applied field was reduced to zero ($`H_{app}`$ = 0) to induce circulating currents in the material (and the magnet was “reset” to provide the quietest and most stable magnetic environment). Then we measured the remanent-state magnetic moment as a function of temperature from 5 K to 95 K in 1 K steps. Complementary field-dependent moments $`m(H)`$, i.e., hysteresis loops, were measured in increasing and decreasing applied magnetic fields in the range from 0 Oe to 30 kOe. The field sweep measurements were conducted at temperatures of 5, 10, 20, 40, 60, 77, and 85 K for each ring. To obtain the critical current density $`J_c`$ from the measured magnetic moments, the critical state expressions Eq. 3-8 were used for each sample configuration.

## IV RESULTS of THE TEMPERATURE SWEEP EXPERIMENTS

For the temperature sweep measurements, each ring was prepared in the critical state by applying a large magnetic field and then reducing it to zero. Two examples of these results for $`J_c(T)`$ in zero applied field are shown in Fig. 1, for a ring containing a 5.1 GB and its companion grain ring. Both have the same $`T_c`$ near 93 K, as did all of the grain, GB, and open rings. For the grain ring in Fig. 1, the current density $`J_c^{Gr}`$ was calculated using Eq. 5. These results are typical of those observed for the companion rings at 5 K in zero applied field, 34-40 MA/cm2. For the GB ring, the current density $`J_c^{GB}`$ was calculated using Eq. 8. As evident in the figure, the values are strongly suppressed relative to those in the grain ring. This is particularly so at low temperatures, where $`J`$ at 5 K in zero applied field lies near 1.6 MA/cm2. (The higher-$`J`$ GB data, shown as filled symbols, were obtained in finite decreasing magnetic field, as will be discussed below). We reported previously Verebelyi01  that corresponding studies of 1.8 GB rings yielded current densities almost identical to those for the grain rings. It was argued that the similarity between the 1.8 GB and its companion grain ring is a consequence of the large numbers of twin boundaries in YBCO thin films.

As the misorientation of the grain boundary increases, the GB current density diminishes significantly. While $`J_c^{GB}`$ is the same as the grain value for a 1.8 boundary, the values at $`T`$ = 5 K fall to $``$ 50 % of $`J_c^{Gr}`$ at $`\theta `$ = 2.8, to 5 % at 5.1, and to 3 % at 7, respectively. Interestingly (and fortunately for coated conductor applications), the *fractional* transport is larger at $`T`$ = 77 K, rising to $``$ 60 % of $`J_c^{Gr}`$ at $`\theta `$ = 2.8, to 15-20 % at 5.1, and to 10 % of $`J_c^{Gr}`$ at 7, respectively. These results show that a small angle c-axis tilt boundary in the range $`1.8^{}<\theta 5.1^{}`$ clearly impedes the current flowing across it. More precisely, the range $`1.8^{}<\theta 2.8^{}`$ contains the critical angle where a grain boundary begins to suppress the current flow across it.

## V RESULT OF THE FIELD SWEEP EXPERIMENTS

The isothermal magnetic response was studied at temperatures $`T`$ = 5 - 85 K. For the grain and open rings, nicely symmetric curves of magnetic moment versus field were obtained, as illustrated by the inset to Fig. 2. The symmetry of the hysteretic $`m`$ about the axis $`m`$ = 0 means that the same absolute magnitude of $`J`$ flows in the ring for increasing field (lower branch) and decreasing field (upper branch) histories. The critical current density was obtained from Eq. 5 and Eq. 3 for grain and open rings, respectively. Typical values were 34-40 MA/cm2 in zero applied field at 5 K. Figure 2 shows the field and temperature dependence of $`J_c^{Gr}`$ for one of the grain rings. The dependence is simple, with a monotonic falloff with both $`H`$ and $`T`$. As in temperature sweep experiments, the in-field features $`m(H,T)`$ for the 1.8 GB and its companion grain ring were nearly identical in field sweep experiments. The curves of $`m`$ versus $`H`$ for the 1.8 and 2.8 GB rings were as symmetric as those of grain rings.

In contrast, the magnetic response of the rings with 5.1 and 7 grain boundaries is considerably more complex. This is evident in Fig. 3, which shows $`m(H)`$ for the 7 ring at several temperatures. Also included for comparison are virgin curves for a representative open ring, which shows the signal produced by a ring with a “grain boundary” of zero conductivity. Qualitatively, the “excess” magnetic moment in the GB ring (larger than the open ring) arises from currents crossing the GB and flowing around the circumference of the ring. The most prominent feature in the $`m(H)`$ curves for the 5.1 and 7 GB rings is the appearance of a large peak in the decreasing field branch; by comparison, the loops for the open ring are symmetric about the $`m`$ = 0 axis, as this signal arises from grain-type currents. Compared with the GB current density in zero applied field, the value at the peak is considerably larger and it occurs at applied fields of several kOe magnitude. To illustrate the difference, the values of $`J_c^{GB}`$ at the peak are included in Fig. 1 as solid symbols.

The appearance of a peak in the GB current density has been reported many times and it is attributed to the effect of a magnetic field on a Josephson junction, which a grain boundary resembles.Evetts88  The occurrence of a peak in the $`m(H)`$ curves of a GB sample, occurring only in decreasing field, marks the appearance of weak-link behaviorShantsev99  in the small angle grain boundary. It is well known that the maximum tunneling current flows across a Josephson junction when the net magnetic flux, which is perpendicular to the tunneling current flow, become zero on the area of the junction. Applying this idea, one expects that the total magnetic field on a grain boundary $`H_{local}`$ becomes roughly zero at the peak in $`J_c`$. Two major fields acting on the grain boundary are the applied magnetic field $`H_{app}`$ and the field $`H_{self}`$ created by induced currents flowing in the vicinity of and parallel to the grain boundary:

$$H_{local}=H_{app}\pm |H_{self}|$$
(9)
In increasing field, the directions of those two fields are the same, giving $`H_{local}=H_{app}+|H_{self}|`$. On the other hand, decreasing the applied field reverses the currents near the grain boundary, giving $`H_{local}=H_{app}|H_{self}|`$ and allowing a cancellation of the applied and self fields. At the peak where $`H_{local}0`$, one has that $`H_{peak}H_{app,peak}|H_{self}|J`$; the last proportionality follows from the fact that $`H_{self}`$ is created by currents flowing near the GB.

Figure 4 tests this scenario by plotting the peak field $`H_{peak}`$ as a function of grain current density $`J_c^{Gr}`$, where both are measured at temperatures from 5 K to 77 K. In Fig. 4a, we consider the simplest approximation that the effective currents have the density $`J_c^{Gr}`$ of the grains, measured in $`H_{app}`$ = 0. This is the most appropriate choice, since grain currents near the GB (where $`H_{local}0`$) contribute most strongly to $`H_{self}`$. Recall that the YBCO film is fully penetrated by flux and that $`J_c^{Gr}`$ is determined in separate measurements on companion rings. Indeed, there is a strong correlation between the peak position $`H_{peak}`$ and the grain current density, as shown by the straight line in the figure with correlation coefficient $`R^2`$ = 0.983. The figure includes data for the weakly linked GBs with $`\theta `$ = 5.1 and 7. To test further the conjecture that a null local field produces the peak in $`J`$, we reduced the current density in two sets of rings while maintaining the same overall geometry; they were partially deoxygenated by annealing in 0.2 bar of O2 at 500 C, followed by furnace-cooling. This decreased $`T_c`$ to $``$ 65 K for the 5.1 GB and 75 K for the 7 GB. Data for those GBs are also included in Fig. 4 (labeled “deOx”) and they follow the same trend as the fully oxygenated rings.

As seen in Fig. 4a, there is a clear correlation between $`H_{peak}`$ and the grain $`J_c^{Gr}`$. One might consider, however, that the appropriate scale of nearby currents is the density $`J_c^{Gr}`$ measured at $`H_{app}=H_{peak}`$. Thus Fig. 4b presents the peak field as a function of this lower, in-field current density. The resulting plot is similar to that in Fig. 4a, with regression coefficient $`R^2`$ = 0.986. Overall, these analyses show that the position of the peaks in $`J_c^{GB}`$ tracks the nearby current density quite well. This supports the conjecture that the peaks correspond to a nulling of the local field acting on a weakly linked grain boundary.

Next we ask whether currents in the film can create local fields comparable with the observed $`H_{peak}`$. This is a difficult question, as it involves the magnetic field very near the edge of a thin sheet of current-carrying superconductor. For one estimate, let us consider the case at $`T`$ = 5 K with grain current density $`J_c^{Gr}`$ $``$ 35 MA/cm2, where $`H_{peak}`$ 2.8 kOe (Fig. 4a). Numerical work of Däumling and Larbalestier Daeumling88  has shown that the perpendicular field is $`\mu _0H1.1\mu _0J_cd`$ (in units of tesla) at the edge of a thin disk with radius/thickness = 103; this expression gives a field of $``$ 1 kOe at the edge of one disk and $`H_{self}`$ 2 kOe, since current flows on both sides of the grain boundary. An alternative estimate comes from the work of Brandt et al., who consider a very long thin strip of type II superconductor in a perpendicular magnetic field.Brandt93  For the parameters cited, their expression for the normal field near the edge of a single strip gives values of 1.2 kOe at a distance $`10\times \xi _{ab}`$ = 15 nm from the edge of the strip, and 1.6 kOe at distance $`\xi _{ab}`$. Doubling these values as above to account for currents on each side of the grain boundary yields self fields $`H_{self}`$ that are very comparable with the 2.8 kOe observed experimentally. While the geometries (disk, edge of thin strip) differ somewhat from the GB geometry, these estimates give some quantitative support for the “null field-weak link” model for the peak in GB current density.

To probe further the grain boundary system near the peak in $`J_c^{GB}`$, we performed minor loop experiments on the 5.1 GB ring at 5 K. The results are shown in Fig. 5a; for comparison, identical measurements on one of the grain rings are shown in Fig. 5b. The following was done. After making a standard $`m(H)`$ loop to 10 kOe and back to $`H`$ = 0, we began to retrace the loop, increasing $`H`$ from low field. Then at 2.2 kOe, the applied field was decreased in 20 Oe steps until the magnetic moment reached the decreasing field branch of the $`m(H)`$ curve. (The orientations of the symbols in Fig. 5 show the direction of field change.) The changes in $`m`$ were very gradual and a field change of at least 100 Oe was needed in order to reach the upper branch. This experiment in the increasing field branch was repeated at 4 kOe with similar results. In contrast, the GB system is much more sensitive in the decreasing field branch: when decreasing $`H`$ from high fields to the peak at 2.6 kOe, an increase of 20 Oe produced a large reduction in the magnetic moment. An increase of only 20 Oe is large enough to switch the magnetic moment almost to the lower branch. At decreasing fields of 1.8 and 4.2 kOe that lie on either side of the peak, the effect is similar although less dramatic at 1.8 kOe where $`J_c^{GB}`$ is smaller. A smaller feature to note is the “foot” where a minor loop rejoins the main $`m(H)`$ curve; particularly noticeable at the lower branch, this component of $`m`$ develops as currents with density $`J_c^{Gr}`$ fully penetrate the “strip-like” portion of the ring.

The major conclusion of the minor loop study is that near the peak in decreasing field, the grain boundaries are very sensitive to a reversal in field-sweep direction. Such a reversal induces oppositely directed perimeter currents in the film and switches the sign in Eq. 9 from ($``$) to (+). Those changes quickly add magnetic flux on the grain boundary, and this degrades the tunneling current across the GB. In contrast, the same experiments on a grain ring give a symmetric response, as illustrated in Fig. 5b. Steps in $`H`$ of 20 Oe give uniform changes in $`m`$, whether increasing or decreasing; the slope $`dm/dH`$ is the same as that at $`H`$ = 0, as is evident from the equally spaced points for $`m`$. The latter is determined almost entirely by the geometry of the ring through its (effective) demagnetizing factor $`D`$. From this perspective, one can consider that the GB ring at its peak has the very large demagnetizing factor of a thin flat ring, but increasing $`H`$ in a minor loop tends to “open up” the GB and reduce $`D`$ to the smaller values more characteristic of a thin strip. This discussion is, of course, only qualitative since some current does flow across the GB. Overall, these minor loop experiments give further support to the picture that the asymmetric, history-dependent $`J_c^{GB}`$ and its peak in decreasing field all originate in the weak-linkage of a grain boundary that is strongly affected by the local field.

Some aspects of the magnetic field dependence remain difficult to understand. In particular, analysis of the magnetic moments in Fig. 3 for increasing field history suggests that the values are about a factor-of-2 smaller than one might expect from estimates of $`H_{local}`$ combined with the observed behavior in the decreasing field branch. This “excess” asymmetry was also observed by Däumling et al.Daeumling92  in transport studies on YBCO bicrystals with higher-angle grain boundaries. Other mechanisms, of course, contribute to the transport of critical currents across grain boundaries. These can include pinning of GB vortices by facets on the boundaryCai98  or pinning of Abrikosov-Josephson vortices on the GB by interactions with (strongly pinned) Abrikosov vortices in the grains.Gurevich94 ; Kim00 . However, none of these other mechanisms readily accounts for a strongly *asymmetric* response, most notably the pronounced peak in the decreasing field branch *only*.

## VI ESTABLISHING the CRITICAL STATE

While the results cited so far were obtained with the entire sample fully penetrated with flux, it is informative to examine how the critical state is established. For these experiments, the films were prepared in the virgin state by cooling them to low temperature in zero applied field. Then the magnetic moment was measured as the field was increased in steps of a few Oe. For the grain films patterned into narrow rings, the magnetic response is rather simple: $`m`$ increases almost linearly with $`H`$ with a slope $`dm/dHa^3`$. This is illustrated in Fig. 6a, where the initial slopes lie within 3 % of the values calculated using Table I of Brandt Brandt97  with (inner radius $`a_1`$)/(outer radius $`a`$) = 1.4 mm/1.5 mm = 0.933. This near-linearity is observed from $`H`$ = 0 up to the field of full penetration $`H_p0.1\times J_cd`$ for this geometry.Brandt97  Full penetration, which is marked by a sudden departure from the nominally linear response in Fig. 6a, occurs at progressively lower fields as $`J_c`$ deteriorates with increasing temperature.

For rings containing a pair of small angle grain boundaries, the initial response is similar. To show this, Fig. 6b presents $`m(H)`$ for a ring with $`\theta `$ = 5.1. Compared with the grain ring, however, there are two qualitative differences. First, the penetration field is much smaller, due to the lower $`I_c`$ of the GB; in the range shown, $`H`$ = 0 - 20 Oe, the film *per se* is little penetrated by flux and the moment $`m`$ is determined almost entirely by circulating currents that cross the GB. Second, further increases in the applied field (above the GB penetration field) immediately reduce the magnitude of $`m`$. Again, this can be attributed to the sensitivity of the GB $`J_c`$ to the *local* field, i.e., applied plus self-field. Experimentally, the GB ring traps no flux until the applied field exceeds the (negative) peak in $`m`$.

Establishing the critical state in an open ring is an interesting contrast. For a thin strip of width $`w`$ and length $`\mathrm{}`$ that the open ring resembles, the magnetic moment is given by Brandt97

$$m(H)=(J_cdw^2\mathrm{}/4c)\mathrm{tanh}(H/H_c)$$
(10)
where the scaling field $`H_c=J_cd/\pi `$ and $`J_c`$ = constant. Figure 7 shows the initial magnetization curve $`m(H)`$ for an open ring at 5 K where, in comparison to the closed ring, the initial slope is much smaller and the approach to saturation is much more gradual. The solid line shows Eq. 10 drawn with the dimensions $`w,d,\mathrm{}`$ of the strip and the current density value $`J_c`$ = 35 MA/cm2 obtained from a full hysteresis loop, giving $`H_c`$ = 22.5 kA/m = 283 Oe. The agreement at low fields is excellent. In larger fields, the theoretical curve lies somewhat below the experimental $`m`$ because $`J_c`$ is not constant, but rather decreases with $`H`$.

Also included in Fig. 7 are the magnetic responses of GB rings with $`\theta `$ = 5.1 and 7, all at 5 K. The initial signal ($`H`$ = 0 - 10 Oe) develops very rapidly; this increase and the subsequent falloff of $`|m|`$ are the same as those shown in Fig. 6b and discussed above. For larger fields $`H`$ 50 Oe, the magnitude of $`|m|`$ again increases. This additional contribution comes from currents induced and flowing entirely within the grain material (not crossing the GB), as evidenced by the fact that the $`m(H)`$ curves for the two GB rings are almost parallel to that for the open ring ’strip,’ but displaced from it. The same phenomenon - generating an additional contribution to $`m`$ by inducing grain currents that are reflected at the GBs - produces the ’foot’ on the minor loops in Fig. 5a.

## VII CONCLUSIONS

Using magntic methods, we have studied current conduction and weak linkage in low angle grain boundaries. Materials investigated were ring-shaped YBCO films with or without -tilt boundaries. Relating the measured magnetic moments to the current configurations in GB, grain, and open ring samples, we obtained the grain boundary current density $`J_c^{GB}`$ from the ring-like contribution to the magnetic moment. The temperature sweep experiments show that a small misorientation $`1.8^{}<\theta 7^{}`$ significantly reduces the grain boundary current density $`J_c^{GB}`$. However, no difference was observed between the 1.8 GB and its companion grain rings. This study suggests that to obtain the highest current density in YBCO thin films and coated conductors with present grain boundary structures, it will be necessary to reduce the c-axis tilt grain boundaries into the range $`34^{}`$. For the 5.1 and 7 GB rings, the $`m(H)`$ (and $`J_c(H)`$) curves have a large peak in finite field, but only for decreasing field history. In small increasing field, the $`m(H)`$ curve of a GB ring resembles that of an open ring. These two results from the field sweep experiments arise from the weak-linkage in moderately low-angle grain boundaries. The high sensitivity of the current density across a GB to field changes on the GB strongly bolsters the weak-link interpretation of low-angle grain boundaries.

###### Acknowledgements.

JRT wishes to acknowledge fruitful discussions with E.H. Brandt, A.A. Gapud, A. Gurevich, H.R. Kerchner, A. Palau, and A. Sanchez. We thank J. Budai for measurement of the grain boundary angles and M. Feldman for providing the 2.8 substrate. This research was performed at the Oak Ridge National Laboratory, managed by UT-Battelle, LLC for the United States Department of Energy under contract No. DE-AC05-00OR22725.

## VIII References


text:
# References

Summary of Spin Physics Parallel Sessions

Jianwei Qiu and Matthias Grosse Perdekamp

> Department of Physics and Astronomy, Iowa State University, Ames, IA 50011
>
> Department of Physics, University of Illinois Urbana Champaign, Urbana, IL 61801 and RIKEN BNL Research Center, Upton, NY 11973

> Abstract. We summarize the activities in the spin physics parallel sessions of the $`8^{\mathrm{th}}`$ conference on intersections between particle and nuclear physics.

Introduction

For spin physics in this conference, we had five parallel sessions and over 500 minutes of presentations. We had twenty-six scheduled talks with twenty-four of them presented at the conference (fourteen in experiment, two in machine and instrumentation, and eight in theory). The talks reported the activities at almost all major high energy spin experiments around the world and covered a wild range of recent theoretical developments in this field. The spin physics parallel sessions had overwhelming participation and were full of exciting discussions.

Polarized parton distributions

The determination of polarized quark distributions, $`\mathrm{\Delta }q(x,\mu )`$, and the gluon distribution, $`\mathrm{\Delta }g(x,\mu )`$, is essential for testing QCD perturbation theory in its spin sector as well as for searching answers to the question on how the nucleon’s spin is distributed among its constituents.

In the framework of QCD, the spin of a nucleon can be expressed as an expectation value of the QCD angular momentum operator in the nucleon state ,

$$\frac{1}{2}=\frac{1}{2}\mathrm{\Delta }\mathrm{\Sigma }(\mu )+\mathrm{\Delta }g(\mu )+L_q(\mu )+L_g(\mu ),$$
(1)
where $`\mathrm{\Delta }\mathrm{\Sigma }(\mu )_q_0^1𝑑x[\mathrm{\Delta }q(x,\mu )+\mathrm{\Delta }\overline{q}(x,\mu )]`$ and $`\mathrm{\Delta }g(\mu )=_0^1𝑑x\mathrm{\Delta }g(x,\mu )`$ are the total quark and gluon helicity, respectively; and $`L_q(\mu )`$ and $`L_g(\mu )`$ are quark and gluon orbital angular momentum (OAM), respectively. The scale $`\mu `$ indicates the momentum scale at which these quantities are measured. Combining all polarized deep inelastic scattering (DIS) measurements, the quark helicity contribution to the proton spin is found to be about $`\mathrm{\Delta }\mathrm{\Sigma }0.2`$ , which is much smaller than the unity expected from the naive quark model. In order to test the sum rule in Eq. (1), we need to measure the individual pieces on the right-hand-side.

The polarized parton distributions (pPDFs), $`\mathrm{\Delta }q(x,\mu )`$ and $`\mathrm{\Delta }g(x,\mu )`$ are nonperturbative but universal quantities, and are not direct physical observables. It is the QCD factorization theorem that connects them to polarized hadronic cross sections via perturbatively calculated partonic hard scattering processes. The pPDFs can be extracted from measurements of polarized cross sections with longitudinally polarized protons.

Until the advent of the RHIC spin program, high energy collisions with longitudinally polarized protons only took place in lepton-hadron DIS. By measuring the double longitudinal spin asymmetry of inclusive DIS cross sections, $`A_{LL}`$, one can extract the structure function, $`g_1(x,Q^2)`$, of the polarized proton,

$$g_1^p(x,Q^2)=\frac{1}{2}\left[\underset{q,\overline{q}}{}\mathrm{\Delta }C_q(x,\alpha _s)\mathrm{\Delta }q(x,Q^2)+\mathrm{\Delta }C_g(x,\alpha _s)\mathrm{\Delta }g(x,Q^2)\right]$$
(2)
where the symbol $``$ represents the convolution over the parton’s momentum fraction and the coefficient functions, $`\mathrm{\Delta }C_i`$ with $`i=q,\overline{q},g`$, are perturbatively calculable. By fitting all available data on the $`g_1`$ structure function for proton and neutron at different values of Bjorken $`x`$ and scale $`Q`$ and using the DGLAP evolution equation to control the $`Q`$-dependence of pPDFs, good constraints on polarized valence quark distributions have been obtained . It was also found that the magnitude of polarized sea distributions are much smaller than that of polarized valence quark distributions and uncertainties on sea distributions are much larger.

The HERMES collaboration improved the separation of quark flavors and extracted the sea and strange quark distributions by the measurement of semi-inclusive DIS (SIDIS) production of $`\pi ^\pm `$ and $`K^\pm `$. With the help of existing quark-to-hadron fragmentation functions, they reported the first determination of leading order (LO) $`\mathrm{\Delta }\overline{u}`$, $`\mathrm{\Delta }\overline{d}`$, and $`\mathrm{\Delta }\overline{s}`$ with the assumption of $`[\mathrm{\Delta }s/s](x)=[\mathrm{\Delta }\overline{s}/\overline{s}](x)`$ . The HERMES collaboration found no significant breaking of the flavor symmetry in the light sea and no indication of a negative strange sea contribution in fits to DIS data . Kretzer in his talk emphasized the importance of good knowledge of the relevant fragmentation functions for the interpretation of these SIDIS measurements . The HERMES collaboration also reports the effort to explore the use of SIDIS $`\mathrm{\Lambda }`$ production for improved sensitivity on $`\mathrm{\Delta }s`$ .

With the high luminosity at the Jefferson Laboratory (JLab), the double spin asymmetry $`A_{LL}`$ in inclusive DIS was measured for the first time in and near the resonance region, from which spin structure functions were measured near $`x=1`$ .

With a very successful 2002 run, the COMPASS collaboration recorded 1.2 fb-1 DIS data with a longitudinally polarized target and 0.3 fb-1 DIS data with a transversely polarized target. Reconstruction of events and data analysis are underway. The COMPASS collaboration expects to have first physics results soon .

The gluon helicity distribution, $`\mathrm{\Delta }g`$, is a key quantity in our understanding of the proton spin. Unfortunately, because gluon contributions only enter the $`g_1`$ structure function at next-to-leading-order (NLO) order and indirectly via the DGLAP evolution, only limited information on $`\mathrm{\Delta }g`$ has been obtained from inclusive DIS measurements. The Asymmetry Analysis Collaboration (AAC) reports that global fits to all existing inclusive DIS data do not provide good constraints on $`\mathrm{\Delta }g(x,\mu )`$ and do not even determine the sign . With the fact that most hard processes at hadron colliders are dominated by gluon initiated subprocesses, the RHIC spin program will provide promising new information on $`\mathrm{\Delta }g`$.

With the proton spin transversely polarized with respect to the collision axis, a novel helicity flip chiral-odd twist-2 quark distribution – known as transversity distribution, $`\delta q(x,\mu )`$, is theoretically allowed . However, there is no leading twist gluon transversity because it would require two units of helicity flip. Since perturbative hard processes conserve helicity, chiral-odd distributions must appear in pairs. That is, transversity can never be measured in polarized inclusive DIS cross sections.

Although transversity can be in principle extracted from the measurement of double transverse spin asymmetries, $`A_{TT}\delta q(x)\delta q(x^{})`$, in jet- or inclusive hadron production in polarized hadronic collisions, the asymmetries are often too small to be extracted experimentally because of the dominance (or lack) of gluonic contribution to the unpolarized (or polarized) cross sections .

Therefore, $`\delta q(x,\mu )`$, is better determined from observables dominated by quark-initiated partonic subprocesses, like $`A_{TT}`$ of Drell-Yan, which unfortunately suffers from the low rate at the luminosities presently available at RHIC. The single transverse spin asymmetry $`A_{UT}`$ in SIDIS between a unpolarized lepton beam and a transversely polarized target is proportional to a combination of $`\delta q(x)\mathrm{\Delta }D(z,𝐤_T)`$ with the Collins’ $`𝐤_T`$-dependent fragmentation function $`\mathrm{\Delta }D(z,𝐤_T)`$ . Transversity distributions could also be accessed by measuring $`A_{UT}`$ in SIDIS in combination with interference fragmentation functions .

Single spin asymmetries in SIDIS

Single spin asymmetries (SSA) in SIDIS between a unpolarized lepton beam and a polarized target can be achieved via the Collins  and Sivers  mechanisms at leading twist or the Qiu-Sterman mechanism  at twist-3. Because of Lorentz invariance of QCD, we need at least four vectors including the spin vector to construct a physically observed SSA. For example, SSAs in SIDIS should be proportional to $`ϵ_{\mu \nu \alpha \beta }q^\mu P^\nu S^\alpha p^\beta `$ where $`q`$ is momentum of the virtual photon, $`P`$ ($`S`$) are momentum (spin) of the polarized target, and $`p`$ is the momentum of the observed final-state hadron. Consequently, SSAs have a unique $`\mathrm{sin}(\varphi )`$ dependence with $`\varphi `$ being the angle between the plane of the three four-vectors ($`q,P,S`$) and the plane of the four-vectors ($`q,P,p`$).

Let $`q`$ and $`P`$ define the collision $`z`$-axis and $`p_T`$ be the transverse momentum of the observed hadron in this frame, then the SSA should be roughly proportional to the dimensionless coefficient: $`p_TM/(p_T^2+M^2)`$ with the typical hadronic mass $`MQ`$ . Therefore, SSAs in general have two distinct regions of phase space: leading twist SSA when $`p_TM`$ and twist-3 SSA when $`p_TM`$. When $`p_T`$ is small, while $`Q`$ in SIDIS provides the hard scale required for the validity of the leading twist approximation, SSAs should be proportional to $`p_T/M`$; and the Collins and Sivers mechanisms lead to nonvanishing SSAs: $`A_{UT}\delta q(x)\mathrm{\Delta }D(z,𝐤_T)+\mathrm{\Delta }f(x,𝐤_T)D(z)`$. The size and sign of the asymmetry are controlled by the nonperturbative $`𝐤_T`$-dependent Collins’ fragmentation function $`\mathrm{\Delta }D(z,𝐤_T)`$ and the $`𝐤_T`$-dependent Sivers’ distribution function $`\mathrm{\Delta }f(x,𝐤_T)`$. When $`p_T`$ is of order of the hard scale $`Q`$, SSAs should be proportional to $`M/p_T`$, a typical twist-3 behavior; and Qiu and Sterman show that the SSA is proportional to new twist-3 tri-parton correlation functions and the corresponding partonic hard scattering pieces can be systematically calculated in pQCD . In terms of final-state interaction between outgoing quark and target spectator, Brodsky et al.  explicitly demonstrated that the Sivers contribution to SSAs in SIDIS does not vanish.

Both the HERMES collaboration  and the CLAS collaboration  observed SSAs in $`e+P(S)e^{}+\pi (p)+X`$ when the target proton spins are oriented either along or perpendicular to the direction of incoming lepton, and verified that both $`A_{UL}`$ and $`A_{UT}`$ are proportional to $`\mathrm{sin}(\varphi )`$. $`A_{UL}`$ is mainly sensitive to the Collins effect while $`A_{UT}`$ should include contributions from both the Collins and Sivers effects.

On the theory side, Gamberg  reported explicit model calculation of SSAs for both $`A_{UL}`$ and $`A_{UT}`$. Afanasev  reported a calculation of a beam SSA. Instead of the target spin vector, the beam SSA is due to a polarized virtual photon on a unpolarized target in SIDIS. The beam SSA is suppressed by an extra power of $`1/Q`$ compared to the SSA from target spin.

Hasuko  reported the status of a program to measure spin dependent fragmentation functions at the Belle experiment in Japan. By measuring the final-state hadron azimuthal asymmetry and correlation, it will be possible to extract the Collins function and possibly other chiral-odd fragmentation functions.

Orbital angular momentum and generalized parton distributions

Asymptotically, the quarks, including both helicity and OAM, carry about 52% of total proton spin while the gluons carry the rest . Since quark helicity contributes about 20% of the proton’s spin, a significant quark contribution to the proton’s spin must come from its OAM . Therefore, knowing the OAM contribution of partons is crucial for understanding the decomposition of the nucleon’s spin in Eq. (1).

Generalized parton distributions (GPDs) share the same operators as normal parton distributions, but are evaluated with a pair of nucleon states of different momenta. GPDs carry much more information than what parton distributions can provide. Belitsky  emphasized that parton orbital angular momentum is directly related to GPDs. He also pointed out that deep virtual Compton scattering (DVCS), recently measured at HERMES, H1 and CLAS, is the cleanest hadronic reaction that gives access to GPDs. The HERMES collaboration reported a measurement of GPDs from SIDIS meson production .

Ji et al.  introduced a phase-space distribution in terms of the GPDs to describe the probability to find a quark at a given momentum and position. Parton OAM plays an important role in determining the phase-space distribution because of its connection to GPDs. The phase-space distribution provides the possibility to study spatial distributions of partons inside a nucleon.

RHIC spin program

The RHIC spin program had its first polarized proton-proton collision two years ago. Two brief polarized proton runs in 2002 and 2003 have resulted in first physics results on transverse spin asymmetries and many important advances in accelerating high current polarized proton beams to high energies as well as proton beam polarimetry at high energies. The main goal of the program is to measure polarized parton distributions, in particular the polarized gluon distribution. However, the combination of available spin orientations and a broad range of experimental processes will also allow to probe the physics beyond the leading twist QCD dynamics as well as beyond the Standard Model.

The STAR Collaboration  has measured the single transverse spin asymmetry $`A_N`$ for pion production both for positive and negative rapidity $`y`$. In the 2003 run, spin rotators were commissioned and for the first time, double spin asymmetries $`A_{LL}`$ were measured in a hadron collider. The data analysis for $`A_{LL}`$ in jet production is in progress and will provide first new information on the gluon helicity distribution . With similar physics motivation, the PHENIX collaboration is carrying out analysis of double spin asymmetries in inclusive hadron production .

In order to improve the figure of merit for the asymmetry measurements, MacKay  argued that it will be possible for RHIC to raise the beam polarization from 35-40% to 70%. He discussed possible methods and plans to improve the luminosity of the polarized beam, which is now about a factor 30 below the design value. Bravar  showed that elastic $`p^{}Cp^{}C`$ has been used successfully as a fast polarimeter at RHIC.

With three DIS machines (HERMES, Compass, JLab) running at different energies and RHIC spin program in a full swing, we will soon have more precise data to cover a wide spectrum of spin physics. A new experiment to test the factorization of SIDIS was just proposed to JLab . Spin physics is getting more and more exciting now!

This work is supported by the U.S. Department of Energy under Grant No. DE-FG02-87ER40371.


text:
# Kinetic Self-Assembly of Metals on Co-polymer Templates

## I Introduction

The field of nanotechnology has seen an explosion of interest over the last decade or so. This has given a big boost to the study of the basic physical phenomena that occur at these small length scales which can be broadly categorized into quantum size effects and interfacial phenomena. The fabrication of materials that are structured at the nanoscale also poses a formidable challenge if we are restricted to conventional lithographic techniques. This has brought to the forefront approaches that use self-assembly to produce ordered structures spontaneously, mostly relying on interfacial and entropic effects, as in the phase separation of diblock co-polymer systems . A natural extension was then to use these self assembled sytems that have structure on the nanoscale as a template, since they have spatially modulated surface properties, to self-assemble the next level of structures .

In this work we examine an experimental realization of the above methodology , where the authors used PS-b-PMMA (Polysterene-Polymethylmethylacrylate ) as a template onto which they deposited various metal films. One might expect that the high surface energy of the metals might dominate the interactions, thus rendering the template irrelevant. However the authors observed a variety of structured morphologies, some that respected the template and others that did not. We show that one can understand the different morphologies based on the relative importance of the kinetics and energetics under the given conditions. We also show that the nature of the kinetics can lead to interesting non-trivial correlations developing in the structures.

We now briefly review the experimental procedure followed by Lopes et al . The template was prepared by first spin coating an ultrathin film of PS-b-PMMA diblock copolymer from solution onto a substrate, which was then subjected to annealing in an inert atmosphere to induce phase separation of the two blocks, producing a fingerprint-like pattern with the two blocks alternating along the film surface. The metals were then evaporated and deposited at room temperature in an inert Argon atmosphere at $`10^6`$ Torr . Fig. 1 shows typical structures obtained with 120 Å of silver as deposited. It depicts the formation of micron-long contiguous wire like structures that run along one of the domains (PS). These structures are remarkably stable (given the high surface tension of silver) and do not break up over a timescale of months.

Following the same procedure for gold, however, does not yield the same results. The gold does not show a high selectivity for the PS domain, but forms clusters in both domains at low coverages and eventually as the coverage is increased, forms large amorphous blobs which ignore the template. To obtain a pattern respecting the template, the authors performed repeated annealing steps (at $`180^o`$ C for 1 min) between depositions of 10 Å gold to induce the diffusion of the gold to the energetically favorable PS domains. Fig.2 shows a typical pattern obtained for 60 Å gold. Note that in contrast to the case with silver no contiguous wire-like structures are formed. Instead, we have “nanochains” of densely packed gold clusters in one domain. It is our intention in this work to understand the energetics and kinetics that govern the self-assembly process and account for the different morphologies.

This paper is organized as follows. In section 2 we show that the wire-like states are non-equilibium states by explicitly computing the free energy. In section 3 we review recent work  on the kinetics of nanocluster coalescence and estimate the relevant timescales in this particular problem. Based on these estimates, we can account for several experimentally observed features including those in other experiments, and the different morphologies encountered. In section 4 we introduce our methods of image analysis that we use to compute the width distribution of the “river” regions between adjacent silver wires as well as the correlations between adjacent silver wires. In section 5 we show how to qualitatively understand these correlations and present our simulations. Finally we compare the simulation results quantitatively, using the river width distribution and correlations, to the experimental results. In section 6 we present our conclusions and scope for future work.

## II Energetic Considerations

We will now ascertain whether the long wire like states of metal described earlier can be equilibrium states. Consider two blobs of metal (silver/gold) that come into contact, as shown in fig.3. The blobs are assumed to be spherical caps (spherical balls with flat bases) with the contact angle being determined by the relevant interfacial energies. The question that we ask is this: do these blobs come together to form a larger blob, or is the difference in interfacial energies on the two phases sufficient to constrain it to form a cylindrical blob (see fig.3)?

To answer this question we first need the relevant interfacial energies. By far the largest of these is at the metal/vacuum interface. The surface energy for a clean gold surface is about 1.35 J/m2 (1.3 J/m2 for silver) . We will neglect any orientation dependence of the surface energy in these estimates. It is to be noted that impurities, or reaction with the atmosphere, can drastically affect these energies, reducing it , in some cases, by almost an order of magnitude . However, since these experiments were done in an inert atmosphere obtained by drawing a high vacuum and then backfilling with inert Argon up to a pressure of about $`10^6`$ Torr, we do not anticipate these effects . In contrast the surface energy for the polymers is very small (about $`34\times 10^3`$ J/m2. The interfacial energy for gold-polystyrene (Au/PS) has an intermediate value of about 0.1 J/m2 . From the difference in mobilities on PS and PMMA, one can estimate the difference in the Au/PS and Au/PMMA interfacial energies. This is done by using the relation $`m\mathrm{exp}\mathrm{\Delta }E/kT`$ , where $`m`$ is the ratio of mobilities and $`\mathrm{\Delta }E`$ is the energetic difference between the two phases for a single adatom. The Au/PMMA interfacial energy is calculated to be approximately 0.3 J/m2. That there is a difference is not surprising since there is strongly suggestive experimental evidence that shows that the interactions at the Au/PS and Au/PMMA surfaces are qualitatively different .

We will now compute the free energies of the two configurations of fig.3 : the cylindrical blob and the spherical blob. Here we assume that only the metal deforms and the substrate remains undeformed. Given that the surface energy of the metal is dominant, one might intuitively expect the spherical final state to be the equilibrium state. We now show this explicitly. We denote by $`\gamma _m`$ the surface energy of the metal and by $`\gamma _{m,PS}`$ ($`\gamma _{m,PMMA}`$) the interfacial energy of the metal PS (PMMA) interface. Since the surface energies of the free polymer are so small by comparison, we neglect them as a first approximation. We denote by $`A_{m,PS}^c`$ ($`A_{m,PMMA}^c`$) the area of contact between the metal and PS (PMMA) in the cylindrical final state and by $`A_{m,PS}^s`$ ($`A_{m,PMMA}^s`$) the same areas in the spherical final state. Note that $`A_{m,PMMA}^c=0`$ (see fig.3). We now denote by $`A_m^c`$ ($`A_m^s`$) the free surface area of the metal in the cylindrical (spherical) final state. The total energy in either final state is then given by

$$E_{c/s}=\gamma _mA_m^{c/s}+\gamma _{m,PS}A_{m,PS}^{c/s}+\gamma _{m,PMMA}A_{m,PMMA}^{c/s}$$
(1)
Taking the spherical blob to be a spherical cap and the cylindrical blob to be a pill shaped object with a flat base and utilising the dimensions in fig 3 and the contact angles derived from the values of the interfacial energies we can compute all the relevant areas. Using these values in the above expression yields

$$E_cE_s10^4kT$$
(2)
with T being room temperature. So we see that the surface tension of the metal indeed dominates and the equilibrium state of two coalescing nanoclusters is the spherical state. Thus the long wire like states appear to be truly non-equilibrium structures. We are now led to ask what the typical timescales are for the equilibration of two coalescing nanoclusters.

## III Kinetic Considerations

The time it takes for metal particles to coalesce, or sinter, is a vital factor in determining the final morphology in growth by evaporation deposition. Conventional approaches to this problem are along the lines of the classic treatment by Herring, Nichols and Mullins . The dominant mass transport mechanism is taken to be surface diffusion driven by gradients in chemical potential which depend on the surface curvature. This kind of treatment assumes that a continuous description is feasible which is possible only when the object under consideration is large enough and has a disordered or rough surface as for a liquid droplet. With these assumptions the authors show that the equilibration time $`t_{eq}`$ scales with the linear dimension $`L`$ of the particle as $`L^4`$, or in other words, as $`N^{4/3}`$, where $`N`$ is the number of atoms. However, for the case of metal nanoparticles at room temperature (below their roughening temperature), it is difficult to see why the above results should still hold.

Recently Combe et al  addressed this very question. They performed Kinetic Monte Carlo simulations of metallic nanoclusters and studied the kinetics of equilibration. They found that at high temperatures close to or above the melting point of the clusters the continuous approach above produces the correct exponent of $`4/3`$ (1.33). However, as the temperature is lowered, the relaxation time remains consistent with a power law scaling with $`N`$ but with the exponent increasing dramatically to about $`5.4`$ at $`400`$ K. They show that the rate-limiting step changes from surface diffusion to the nucleation of new terraces of atoms on facets that appear as the temperature is lowered below the roughening temperature. It is to be noted that the sintering of two contacting grains is not limited by terrace nucleation and should thus be fast.

We will now estimate the relevant time scales in our problem using the phenomenological law

$$t_{eq}N^q$$
(3)
with the values for the temperature-dependent exponent $`q`$ obtained in . For a metal (gold) cluster with about $`N_0=10^3`$ atoms at $`800`$K, the equilibration time is about $`100`$ ns . In comparison, the prediction from the macroscopic theory gives a time an order of magnitude lower even for a relatively small cluster such as this. We take this timescale, $`\tau _0=100`$ ns to compute the the equilibration times for larger clusters. As a first approximation we neglect the effect of temperature on $`\tau _0`$, i.e., we assume that a $`1000`$ atom cluster takes roughly the same time to equilibrate even as the temperature is lowered, which will be increasingly true as the cluster size is reduced.

We next look at a typical cluster in our problem. Fig 4 shows typical clusters that are obtained at low coverages. Given that the width of the PS domain is about 25 nm, we see clusters that are about 10-12 nm in diameter. Two of these that are beginning to coalesce will contain about $`N=10^5`$ atoms. The equilibration time, at $`T=400`$K for example, can now be computed using the scaling law.

$$t_{eq}=\tau _0(N/N_0)^q$$
(4)
Using the values $`N=10^5`$, $`N_0=10^3`$ and $`q=5.4`$ at $`T=400`$K we get $`t_{eq}2`$hrs. Thus, even at $`400`$K, the equilibration time can run into hours. Extrapolating the value of $`q`$  to room temperature can give values as high as $`q7`$, which translates into equilibration times of many months. The two other timescales that are relevant are the time it takes for two typical clusters to find each other ($`t_f`$) and the timescale of the deposition process. The deposition process typically takes a few minutes and is hence a much smaller timescale. Using typical values for cluster diffusion constants in such situations  , $`D10^{14}`$ cm2/s and a typical separation, $`l`$, of the order of nanometers, we may estimate $`t_f`$

$$t_fl^2/D1sec$$
(5)
Hence $`t_ft_{eq}`$.

Since the coalescence time is much greater than the typical time for the clusters to find each other, we must necessarily anticipate the growth of extended non-compact structures. In the case of the silver being deposited on the PS-b-PMMA template, the difference in mobilities of the silver on the PS (low) and PMMA (high) implies that the silver is quickly made available over the energetically favorable PS domain where it tends to stay. This in turn implies that the non-compact structures we anticipate will lie along the PS domains, resulting in, as observed experimentally, long wire-like states on the PS phase (as in fig 1). The argument above is quite general and should apply to any metal that shows sufficient overall moblity and energetic preference for one of the two phases. However, Lopes et al observed that for gold, following the same procedure did not form wires. They found that gold as evaporated and deposited at room temperature did not show sufficient selectivity which led to the occurence of large clusters on the PMMA phase which were almost immobile. Further deposition did indeed lead to non-compact objects but which had no directional preference, thus forming patterns that ignored the template. Lopes et al tried to obviate this problem by annealing at 250 Celsius in between deposition steps so as to get the gold to diffuse to the energetically favorable PS domain. From our arguments about the kinetics we presented, it becomes clear that doing so will dramatically decrease $`t_{eq}`$, resulting in equilibrium spherical structures. Indeed, this is what they observed, as shown in fig. 2. The situation was further complicated by the fact that during annealing gold also diffuses into the bulk, reducing the amount of gold at the surface.

Another interesting observation is that the micron long wire-like states of silver, when annealed at a slightly elevated temperature (90 Celsius) for about 3 hours, break up and “ball up”, ignoring the template as in fig.5. This temperature is below the glass transition temperature of the substrate and the melting temperature of the silver. Thus, this phenomenon seems to point to the fact that these structures are indeed non-equilibrium states. From our estimates of the relevant timescales the reason for this phenomenon becomes apparent. Raising the temperature to about 400 K changes the equilibration time $`t_{eq}`$ from months to hours. Therefore waiting at the elevated temperature for a few hours will indeed result in observable changes in the morphology as the system moves toward equilibrium.

Now that we have a qualitative understanding of how these wire-like states are formed, we will focus on certain characteristics of these states. We will show that there exist non-trivial correlations between adjacent wires and further, that these can be understood as arising from a kinetic mechanism.

## IV Correlations

Looking closely at the silver wires (fig.1) one suspects the presence of correlations between adjacent silver wires. If we designate by the term “river”, the silver free PMMA regions in the picture and by the term “bank”, the boundary of the silver-PMMA interface, then an outward bulge on one bank seems to correspond with an inward depression on the opposite bank. It is to be noted that the underlying PS-PMMA interface is relatively smooth, so that the bumps are merely on the silver structures. The presence of correlations, if true, is significant because it might imply that there is an interaction between the banks whose origins may be electrostatic or even mechanical (strain mediated by the substrate). This might be an alternate explanation for the stability of the wires. We will show, however, in the next secton that the observed correlations can be accounted for simply by a kinetic mechanism. We now attempt to measure these correlations to see if they indeed exist and to quantify them if they do.

As a first attempt to quantify the correlation we look at the simplest statistic which could yield some information, namely, the river width distribution.

We first map the TEM images (see fig. 1) to an image with binary values for the pixels. A pixel has a value 1 if the corresponding point in the image has silver and a value 0 if it does not. We are then left with an image that is shown in fig. 6. The rivers are now pixels with value zero. We now wish to ascertain the midpoints of the river, i.e., points that are “equidistant” from either shore. It is not a priori obvious how one can rigorously define the midpoints of the river regions since the rivers curve (following the underlying PS-PMMA domains) thus making it difficult, given one point on one bank, to pick out a corresponding point “across” the river. We tackle this problem as follows. For each point $`P`$, in the binary image with pixel value zero (a point in the river), we find the closest point on either bank. We denote the distance by $`r`$. Next we compute the average pixel value in a circle of radius $`2r`$ around point $`P`$ and assign this value to the point. Now it is to be noted that the value assigned increases as the point moves further from one bank. It reaches a maximum somewhere in the middle and then begins to decrease as the oppposite bank is approached. This is done for all points with pixel value zero. We thus generate an image with all the pixels in the river regions having non-zero values assigned to them, with values being largest in the middle of the rivers. By appropriate thresholding we can get a line of points running down the middle of the river which we denote as the “set of midpoints” of the river (see fig.7). Knowing the value of $`r`$ associated with each of these points we can plot a distribution of river widths. Fig.8 shows a distribution obtained from data from four images such as the one in fig.6. The average width is 8.24 nm and the standard deviation is 2.6 nm.

We now construct a “control” case where the two banks are explicitly uncorrelated. We do this by considering three adjacent strips (see fig.9) each representing a width of $`25`$ nm and a length of $`500`$ nm. The two outer regions represent PS domains and the one in between is a PMMA domain. We then put down spherical silver clusters of a fixed radius at randomly chosen nucleation points in the PS domains. The clusters are allowed to overlap and by adjusting the density of nucleation points as well as the radius of the spheres we can get contiguous wire-like structures on the PS domains. In reality, the surface tension of silver will tend to smoothen the surface. We model this by a smoothening algorithm which allows material from regions of high curvature to flow to those with low curvature. This algorithm is run till the surface is smooth, i.e., there are no obvious discontinuities in the derivative of the curve representing the silver-PMMA boundary yielding wire-like structures separated by silver free “river” regions, as in fig.9. The density and radius are chosen so that the “bumps” of the wires have roughly the same magnitude as in the experimental situation. It is to be noted that the “bumps” on either side (bank) of the silver free PMMA region are uncorrelated by construction. The width distribution of the control case is shown in fig.10. The average width is 9.53 nm and the standard deviation is 2.7 nm. Though the numbers are not very different, comparing the two width distributions (see fig.11) shows that the distribution for the control case is broader and more symmetric while the experimental distribution is narrower with a steep rise and a more gradual fall-off for increasing width. If the two banks meandered in unison one would indeed expect a qualitatively narrower width distribution. Thus the “narrowness” of the distribution qualitatively indicates the presence of correlations.

In order to pin down the extent of correlations quantitatively, we now define a new statistic, as follows. For every point in the set of midpoints we identify two corresponding points, one on each bank. This is done by constructing a normal to the local tangent of the line of midpoints. The intersection of the normal with each bank gives us one point, thus yielding a pair of points on opposite banks for each midpoint. We then compute the local curvature of the bank at each point of this pair and assign to the midpoint, the product of the curvatures. It is to be noted that the product, which we will denote by $`C`$, will be (a) zero : if the bank on either side is locally straight, (b) negative : if the banks curve away from each other and (c) positive : if the banks curve “together” in the same direction. The last case is what we mean when we say “correlated”. Thus we generate for each midpoint a value based on the correlation of the local curvatures of two banks nearby. We then assign to each midpoint the average value of $`C`$ of all the midpoints within a distance equal to the local width. Fig. 12 shows a histogram of the values of $`C`$ thus obtained. At first it might appear that positive and negative correlation contributions are the same. However, replotting the histogram with the difference between the positive and negative contributions at a value of the absolute magnitude of $`C`$ versus $`C`$ shows a clear trend for the excess of positive contributions (see fig.13).

Figure 14 shows a plot of the same statistic ($`C`$) for the control case. In this case there seem to be more negative than positive contributions. Figure 15 allows us to compare the difference between the positive and negative contributions for the experimental and the control case. Here $`C`$ for each case has been scaled by the square of the average width of the width distribution for that case, so as to obtain a dimensionless quantity, which can then be compared. The quantity $`f_+f_{}`$ is the fraction of data points with a value $`+Cw^2`$ less the fraction of points with a value $`Cw^2`$. We immediately see a striking qualitative difference between the experimental case with mostly positive values and the control case with predominantly negative values over the same range of values of $`Cw^2`$ indicating that there are indeed non-trivial correlations between the banks.

Does the presence of non-trivial correlations between the wires imply a stabilizing interaction between the wires or do these arise simply from the kinetics of the wire formation process? It is precisely this that we will address in the next section.

## V Accounting for Correlations

An important clue is the fact that even for silver, which shows an almost 100% selectivity at low coverages, there are still some clusters in the PMMA domain (see fig. 4). This implies that clusters do nucleate and grow in the PMMA domain as well. We later show that simulations with the right diffusion constants do indeed lead to cluster formation in the river regions. Now let us consider a later stage in the process when the basic wire-like states have already been formed, while deposition still continues. Clusters in the river regions will grow due to the incident flux of silver atoms and new clusters will also be formed. As the clusters grow bigger they slow down and explore a more restricted region. Eventually a big cluster will diffuse to one of the two banks in its vicinity thus leading to enhancement of material (a bump) on one bank at the expense of the nearest regions of the opposite bank. Thus this kinetic process leads to the development of correlations between the two banks. We now present simulations of a model of the process to see if we can quantitatively account for the correlations measured in the previous section.

We first need to know the diffusion constants for silver clusters in the PMMA region. To do this we refer to the experiments done on the evaporation deposition of silver on homopolymer PMMA and PS . For low coverages of silver the author measured both the nearest neighbor distance distribution, as well as the size distribution of the resulting islands at a given flux rate. We performed simulations by considering a square region with periodic boundary conditions that represented a $`250\times 250`$ nm2 section of the homopolymer substrate. We modeled the flux of silver by the introduction of small clusters (about 100 atoms) at the appropriate rate which were then allowed to diffuse with a predetermined diffusion constant $`D_0`$. Clusters were allowed to coalesce upon contact, forming larger spherical islands. The diffusion constants of larger clusters were assumed to follow a $`N^{2/3}`$ law . By suitably adjusting the value of $`D_0`$, we were able to match both the distributions measured experimentally. This gave us a value of $`D_0=10^{13}`$ cm2/s for the diffusion constant of the small silver clusters on PMMA. This value is consistent with values for cluster mobility on organic substrates , which are typically of this order. Now that we have fixed the value of the diffusion constant we present our simulations that attempt to capture the correlations.

To this end we consider a rectangular region which represents a $`500\times 25`$ nm2 section of the substrate. This section represents a PMMA domain of width $`25`$ nm and length $`500`$ nm. The boundary conditions are periodic in the long direction. In the short direction, the boundaries are meant to represent a solid silver wall, mimicking the edges of silver wires on the PS domains. Thus a cluster touching these boundaries sticks there and is assumed to be immobile, though it can still grow from the incident flux of silver. The procedure is exactly the same as for the homopolymer case described above. Clusters are incident on the river region at the appropriate flux (set by the experimental value) which then diffuse and coalesce, and eventually stick to the banks on either side. As mentioned before, we do indeed see the formation of large clusters ($`10^4`$ atoms) that have not yet been trapped by the walls. We do not know how long the late stage of the process is, so we take a conservative underestimate by continuing the deposition till about 50 % of the PMMA region is covered. This is to be contrasted with the coverage in the experimental case which is about 66%. By underestimating the coverage we hope to produce a conservative estimate for the correlations which is still comparable to the correlations in the experimental case. Once the deposition and diffusion process is over we get a series of bumps on both banks of the river region where the clusters have stuck. We then smoothen the surface by the algorithm described in the previous section for the control case. A typical image thus obtained is shown in fig.16. A casual inspection shows that the correlations we noticed in the experimental images seems indeed to be present in these images. To quantify this we analyze the simulated images exactly as we did the experimental images and the control case by the method described in the last section. The width distribution obtained is shown in fig.17. We notice that it looks very similar to the experimental case (see fig.11 for comparison) except that it is slightly shifted to the right (larger mean width) due to the underestimation of the coverage. Fig.18 shows the plot for the correlations. The plot looks qualitatively similar to the histogram for the experimental case (fig.12). Fig .15 shows the plots of $`f_+f_{}`$ for the experimental, simulation and control cases. We see that the simulation results are in good agreement with the experimental results, both of which are qualitatively different from the plot for the control case. Thus, one can reproduce both qualitatively and quantitatively the correlations observed in the experiment with a simple kinetic mechanism.

## VI Discussion of Results

We have presented an analysis of the energetics and kinetics that govern the self-assembly process of metals on patterned polymer templates. We have shown that depending on the conditions one can have one or the other dominating the process. Thus tuning the conditions can lead to vastly different morphologies as evidenced by the experiments. In our analysis the only factor that depended critically on the nature of the metals was the selectivity between the two domains. One could then, in principle, form wire-like states of different metals provided there is a sufficient contrast in mobilities and an energetic preference for one of the domains. It is to be noted that achieving this by raising the temperature will have the effect of driving the system to equilibrium (spherical clusters) as seen in the case with gold. This could be done on the other hand by changing the composition of the underlying domains. Tuning the composition to such an extreme that the metal-polymer interfacial energy becomes comparable to the metal-air interfacial energy can, of course, lead to equilibrium structures with the metal wetting one domain and dewetting from the other and forming wires. However, such an extreme is not necessary and may not even be possible with conventional polymer systems. We only need to enhance the contrast in mobilities and the energetic difference and kinetics will take care of the formation of the wires. Another interesting aspect we presented was the presence of correlations stemming from the kinetics of the self-assembly process. We measured these correlations and showed that a simple simulation that captured the essential features of the process could indeed give correlations comparable in magnitude. Finally, we see that one could, in principle, tune the correlations by increasing or reducing the flux since cluster formation in the river regions depends on the flux.

Another aspect that would be useful to study is the role of grain boundaries, which has been neglected in this study. Since the wire states are polycrystalline in nature the presence of the grain boundaries will affect the stability of the structure. Another avenue of interest would be to do a more realistic simulation of the entire process, which could shed light on the distribution of sizes of nanocrystalline domains in the wires.

The present model appears to provide a basic understanding of the mechanism of spontaneous wire formation on striped copolymer templates. It identifies general kinetic criteria for the formation of wires. By meeting these criteria, we expect to find ways of forming such wires with a variety of metals. Further, our new understanding of the correlations has led to insight about why the wires are irregular and a strategy to reduce this irregularity.

## VII Acknowledgements

The author would like to thank Tom Witten, Ward Lopes, Heinrich Jaeger, Bob Gomer, Stuart Rice, Ruoyu Bao, Li-Sheng Tseng, Dan Robbins, Toan Nguyen and members of the Witten group for insightful discussions and comments. This work was supported in part by the National Science Foundation under award DMR-9975533 and via its MRSEC Program under Award Number DMR-0213745.