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# Defect Formation and Kinetics of Atomic Terrace Merging

## I Introduction

Structural phase transitions on stepped metals have gained much attention in recent years. Starting from some of the first experiments by Lang et al  who noticed single height steps merging to form double height steps on Pt{544} to time lapsed STM measurements of the dynamics of the step doubling process more recently  the field has been attracting more attention. The study of surface structure and in particular the formation of defects during the step doubling process is important as these influence the desirable technological properties of the surfaces. Various experimental  and theoretical studies  have been performed to elucidate the dynamics of the evolution of these step doubling processes. However one major aspect that has been missing from the theoretical endeavours is to characterize the evolution of defects in these processes. One of our main motivations is to address this question theoretically.

An important characteristic of the step doubling process is that, under the optimal conditions, it is manifestly non-equilibrium. Steps seem to double irreversibly (unless conditions are changed) and hence equilibrium statistical mechanics treatments are suspect. The problem is thus a part of a whole set of interesting problems. These include non-equilibrium epitaxial growth models, many of which are described by the Kardar-Parisi-Zhang equation . Irreversible depositon of macromolecules on surfaces and sociological epidemic models  also fall in this category. Our approach to treating the step doubling process is derived from treatments of random sequential adsorption (RSA) problems  which deal with irreversible adsorption of objects onto lattices.

In this paper we consider a simple model  for the step doubling process described by two parameters, a nucleation rate and a zippering rate. We first map this problem onto a one dimensional random sequential adsorption problem with two kinds of species adsorbing onto the lattice corresponding to perfectly doubled steps and defective structures. We then utilize the methods of RSA to solve the problem analytically. We are able to make predictions for the fraction of defects and perfectly doubled steps in the asymptotic stages of the process. We also predict the dynamical evolution of the degree to which the surface has undergone doubling. The theoretical predictions are then checked against extensive simulation results and found to be in good agreement. We finally make contact with experimental results and show how our analysis can be used to extract information about the dynamics of the process.

The paper is organized as follows. We first introduce our model for the step doubling process which utilizes a coarse grained picture of the surface. We then solve the problem in the special limit where the zippering rate is infinite by mapping it exactly to the problem of random sequential adsorption of dimers on a 1-D lattice. We then step back and set up the general mathematical framework for random sequential adsorption of more than one species. We then use this framework to tackle the problem of accounting for defects. We then generalize this to the case where our field of view does not encompass the whole sample but just a part of it, since this is closer to the experimental situation. We then discuss the time dependence of the surface morphology. Next we present our simulation methods and we finally conclude by discussing our results.

## II Theoretical Analysis

It is found that steps commence coalescing at a point contact where a step edge bulge touches the neighboring step edge below it (see fig. 1). This is called a nucleation event. Once a nucleus has been formed the two steps begin coalescing steadily in both directions from the nucleus. This process is referred to as zippering. Thus there are two distinct rates that govern the formation of the doubled structure, the nucleation rate $`I`$ (defined as the number of nucleations that occur per unit time on a sample that has no doubled steps) and the zippering rate $`Z`$ (defined as the rate of change of the length of a doubled step in units of the step width). This zippering rate is observed to be large enough that many steps undergo complete doubling. Our analysis will focus on this regime of small $`I/Z`$.

When the step doubling process has reached its final state two main kinds of defects are observed to remain. The first kind are isolated step edges whose neighbors to both the right and left have doubled with their other neighbors leaving the step “isolated” (see fig. 1). The second kind are frustrated dead ends which are formed when a step merges to its left at one point along the step and to its right at another point. We wish to understand how the nucleation and zippering rates affect the formation of these defects.

### A Final State

The simplest model assumes that nucleation points occur randomly over the entire sample with a probability per unit time determined by the nucleation rate ($`I`$). The steps then coalesce at a steady rate ($`Z`$). To attack this problem we first imagine mapping a square section of the sample to a coarse grained lattice (see fig. 1). Here each column represents a step. A lattice site can either be occupied or unoccupied. Occupied sites represent sections of a step that have doubled. A step is allowed to double only with its downstairs neighbor (to the right as in fig. 1). Thus occupied lattice sites occur in pairs, one each on adjacent steps. A nucleation event where a step edge bulge touches its downstairs neighbor is represented as shown in fig. 1 in the coarse grained picture. Taking the coarse grained view involves the loss of some specific information about the system. One loses information about the exact position of a nucleation point and also the exact shape of the doubling step. Positions in the vertical and horizontal direction can only be specified up to a single step width. Thus the coarse graining will also fail to capture the meandering of individual steps.

Once a nucleus has been formed the two steps will eventually form a double step unless it gets frustrated as described previously (and in fig. 1). If we examine the system after all evolution has ceased, there are thus at least two possible entities: a perfectly doubled step which occupies two columns of the coarse grained lattice and a frustrated pair which occupies three columns. There are in principle higher order defects that can occupy more columns (see fig. 2). For example one can have an extended structure where the doubling of steps 1 and 2 is frustrated by the doubling of steps 2 and 3 at another point which in turn is frustrated by steps 3 and 4 nucleating a doubling event and so on. To be able to proceed with an analysis we need to understand what kind of defects are important and under what conditions. We first consider the simplest case where the zippering rate is taken to be infinite.

### B Infinite Zippering Rate

In this case the nucleation rate, $`I`$, is assumed to be some finite number while the zippering rate, $`Z`$, is taken to be infinite. Now any nucleation will lead to a perfectly doubled step as the steps zipper together instantaneously. There will be no frustrated dead ends in this scenario. However there will be isolated steps, both of whose neighbors have doubled with other steps. The question then is how many of these isolated steps will be present in the final state when all evolution is complete.

To answer this question, we first note that a nucleation attempts the occupation of two columns in the coarse grained lattice picture. If the columns are unoccupied before the attempt, the nucleation is successful and both columns are occupied. Thus in any given time step when a succesful nucleation occurs two adjacent columns are fully occupied. Furthermore once these columns have been occupied subsequent successful nucleations cannot overlap either of these columns. We can now visualize the process as occuring on a 1D lattice each site of which corresponds to a column on our original lattice. A successful nucleation event leads to the occupation of two consecutive sites on this 1D lattice. Each nucleation attempt therefore corresponds to a random choice of a pair of consecutive sites. If both these sites are unoccupied, the attempt is successful and as a result both the sites are occupied. This process is exactly random sequential adsorption (RSA) of dimers (objects that occupy two lattice sites) onto a 1D lattice. In the RSA process a dimer attempts to adsorb onto the lattice at every time step, corresponding to the nucleation attempts in our system. Dimers cannot overlap just as in our system already doubled steps cannot double again with a different step. Thus in the limit of an infinite zippering rate our problem maps exactly to an RSA problem of dimers adsorbing onto a 1D lattice.

Though the solution to the RSA problem is standard , we present the solution for completeness and to set the stage for the next subsection. We first define $`P_n`$ to be the probability that a randomly chosen site is part of a sequence of at least $`n`$ consecutive empty sites. We can then write down the time evolution of this probability for $`n1`$

$$\frac{dP_n}{dt}=k(n1)P_n2kP_{n+1}$$
(1)
The first term accounts for the sequence being broken by the adsorption of a dimer within the $`n`$ sites, which can be done in $`n1`$ ways. The second term refers to a dimer overlapping the sequence from either end if the sequence has at least $`n+1`$ sites. This can be done in two ways. In order to solve this set of equations, we first define the conditional probability $`g_n=P_n/P_{n1}`$. Using equation 1, we can write down the set of equations satisfied by the $`g_n`$’s.

$$\frac{dg_n}{dt}=kg_n2k(g_ng_{n+1}g_n^2)$$
(2)
Now at time $`t=0`$, the lattice is empty and all the $`P_n`$’s are identically unity. This implies that all the $`g_n`$’s are unity at $`t=0`$. Therefore the initial conditions tell us that all the $`g_n`$’s satisfy the same equation at $`t=0`$ since the second term on the right hand side in equation 2 does not contribute. However this means that as time progresses the $`g_n`$’s evolve in an identical fashion, all of them being equal, with the second term never contributing. Thus $`g_n=f(t)`$ is simply a function of time and does not depend on $`n`$. We can therefore look for solutions to equation 1 of the form

$$P_n=f(t)P_{n1}$$
(3)
Using this with eq.(1) gives a differential equation for $`f(t)`$ (which can also obtained directly from eq.2) that may be solved to yield the ansatz

$$P_n=e^{k(n1)t}P_1$$
(4)
It may be readily verified that the ansatz consistently satisfies eq.(1). Now using (1) and (4) we get

$$\frac{dP_1}{dt}=2ke^{kt}P_1$$
(5)
which yields

$$\mathrm{ln}P_1=2e^{(k)t}+c$$
(6)
where $`c`$ is an arbitrary constant. Using the initial condition that at $`t=0`$, the lattice is empty and hence $`P_1=1`$ we get

$$c=2$$
(7)
We thus have an explicit solution for $`P_1`$

$$P_1=\mathrm{exp}[2e^{(k)t}2]$$
(8)
This tells us that when $`t\mathrm{}`$, $`P_1e^2`$. The fraction of sites that are unoccupied in the final state is therefore $`e^213.5\%`$. Thus even in the case where we only have perfectly doubled steps the percentage of total area covered by the doubled steps is $`86.5\%`$. There will always be $`13.5\%`$ of the surface covered by isolated single step defects. In the case of a finite system we expect $`13.5\%`$ defective area on average. We will later consider the case where the ratio $`I/Z`$ is small but finite. Here we expect not only isolated step edges but also frustrated dead ends and possibly defects of higher order.

### C Accounting for frustrated dead ends

In real experimental situations , one observes not only perfectly doubled steps but also frustrated dead ends (defects of order one). In this section we will lay down the mathematical framework, which we will use to treat the occurence of defects. Suppose we are in a regime (low $`I/Z`$) where we have only two significant entities: perfectly doubled steps and frustrated dead ends. A perfectly doubled step occupies two columns and a frustrated dead end spans three columns. We may now think of the process as occuring on a 1-D lattice with dimers (blocks of two lattice units) representing perfectly doubled steps and trimers (blocks of three lattice units) representing frustrated dead ends adsorbing onto the lattice at different rates. The dimer attempt rate is denoted by $`k`$ and the trimer attempt rate by $`k^{}`$. These attempt rates are in general functions of time, the nucleation rate and zippering rate. The problem of determining these attempt rates will be dealt with in the next section. For now we take them to be arbitrary functions of time. The kinetics of this process corresponds to the problem of random sequential adsorption (RSA) of a binary mixture  though with attempt rates that are functions of time. As before we first define $`P_n`$ to be the probability that a randomly chosen site is part of a sequence of at least $`n`$ consecutive empty sites. We can then write down the time evolution of this probability for $`n>2`$

$$\frac{dP_n}{dt}=k(n1)P_n2kP_{n+1}k^{}(n2)P_n2k^{}P_{n+1}2k^{}P_{n+2}$$
(9)
The first term accounts for the sequence being broken by the adsorption of a dimer within the $`n`$ sites, which can be done in $`n1`$ ways. The second term refers to a dimer overlapping the sequence from either end if the sequence has at least $`n+1`$ sites. This can be done in two ways. The third, fourth and fifth terms are similar to the first and second except that they refer to the adsorption of trimers in an analogous fashion. Introducing the conditional probabilities $`g_n=P_n/P_{n1}`$ and using the initial conditions, we find that $`g_n=f(t)`$ is only a function of time and does not depend on $`n`$. We therefore introduce the ansatz

$$P_n=f(t)P_{n1}$$
(10)
Using this in conjunction with equation (9) and the initial condition $`P_n=1`$ yields

$$f(t)=e^{_0^tk(t^{})+k^{}(t^{})dt^{}}$$
(11)
This along with equations (9) and (10) yield an explicit solution for $`P_2`$

$$P_2=\mathrm{exp}\left[_0^tk(t^{})𝑑t^{}_0^t[2f(t^{})(k(t^{})+k^{}(t^{}))+2k^{}(t^{})(f(t))^2]𝑑t^{}\right]$$
(12)
and hence from (10) for all $`P_n`$ for $`n2`$. For $`n=1`$ we have

$$\frac{dP_1}{dt}=2kP_23k^{}P_3$$
(13)
which upon integration gives

$$1P_1(t=\mathrm{})=_0^{\mathrm{}}(2kP_2+3k^{}P_3)𝑑t$$
(14)
$`P_1(t=\mathrm{})`$ is simply the fraction of space occupied by isolated dead ends at asymptotic coverage. The two terms on the right are simply the fraction of space occupied by the dimers (double steps) and trimers (frustrated dead ends) respectively. It is to be noted that this constitutes an exact solution for the problem of random sequential adsorption of a binary mixture in 1D with arbitrary time dependence of the attempt rates. It is also to be noted that this analysis may be extended to include defects of higher order if one knows the attempt rates for all the species being considered. We now consider the case with $`I/Z`$ small but non-zero and compute the rates $`k`$ and $`k^{}`$ explicitly in terms of the experimental parameters $`I`$ and $`Z`$.

### D Nonzero but Small I/Z

We now apply the formalism developed in the previous section to our problem where we are given the experimental parameters: the nucleation rate $`I`$ and the zippering rate $`Z`$. The case when $`I/Z`$ is small but non-zero is important as it is closer to reality. Most experimental situations have $`I/Z`$ values which are typically of order $`10^3`$ to $`10^1`$ . To begin our analysis we need to understand for what values of $`I/Z`$ different orders of defects become important. Intuitively one expects that for small enough $`I/Z`$, considering only defects of order one would be a good approximation. To estimate how small $`I/Z`$ needs to be we first consider the mean free path, $`l`$, of a successful nucleation on an empty lattice. By mean free path we mean the average length to which the doubled step grows before it is cut off by other nucleations.

Heuristically one can say that higher order defects will not be important when the mean free path is much larger than the size of the lattice we are dealing with i.e. $`lM`$. We now focus on a regime of low $`I/Z`$ that satisfies the above condition with the assumption that we only have frustrated dead ends. The explicit condition will be worked out later in this section.

We can now view the whole process as occuring on a 1-D lattice of size $`M`$ corresponding to the problem of random sequential adsorption (RSA) of a binary mixture. In our system there are only dimers trying to adsorb onto the lattice except they may turn into a trimer if another dimer overlaps one of its units within the time it takes to zipper $`M`$ steps. We thus view this as a RSA process with the rate at which trimers try to adsorb determined by the probability, $`q`$, of the above mentioned overlap occuring. We now compute this probability explicitly in terms of $`I`$ and $`Z`$.

We first define $`q`$ to be the probability that a nucleation event leads to a perfectly doubled step on an empty lattice. If $`I`$ is the nucleation rate over the $`M\times M`$ sample then the probability of any one element initiating a nucleation in time $`\mathrm{\Delta }t`$ is $`I/M^2\mathrm{\Delta }t`$. Now consider a nucleation event $`k`$ lattice constants away from the nearest horizontal edge of the $`M\times M`$ lattice (see fig. 3).

Upto a time $`t_a=2k/Z`$, both ends of the doubled step grow by zipping. For $`t>t_a`$ only one end grows since the other end has already reached the edge of the lattice. This part of the process takes a time $`t_b=2(M2k)/Z`$. For $`t<t_a`$ the number of sites where a nucleation can lead to frustration is $`2(MZt)`$. For $`t_a+t_b>t>t_a`$ the number of sites where a nucleation can lead to frustration is $`2(M2kZ(tt_a)/2)`$. Now the probability at a time $`t_i<t_a`$ past a nucleation that the doubling steps do not get frustrated in the next $`\mathrm{\Delta }t`$ of time is given by

$`P_a(i)`$ $`=(1{\displaystyle \frac{I}{M^2}}\mathrm{\Delta }t)^{2(MZt_i)}`$ (15)
$`\mathrm{exp}\left[{\displaystyle \frac{I}{M^2}}2\left(MZt_i\right)\mathrm{\Delta }t\right]`$ (16)
Similarly for $`t_a+t_b>t_j>t_a`$, we get

$`P_b(j)`$ $`=(1{\displaystyle \frac{I}{M^2}}\mathrm{\Delta }t)^{2(M2kZ(t_jt_a)/2)}`$ (17)
$`\mathrm{exp}\left[{\displaystyle \frac{I}{M^2}}2\left(M2kZ\left(t_jt_a\right)/2\right)\mathrm{\Delta }t\right]`$ (18)
Thus the total probability that the nucleation event, $`k`$ lattice constants from the edge, leads to a perfectly doubled step is

$`q_k`$ $`{\displaystyle \underset{i}{}}P_a(i){\displaystyle \underset{j}{}}P_b(j)`$ (19)
$`{\displaystyle \underset{i}{}}\mathrm{exp}\left[{\displaystyle \frac{I}{M^2}}2\left(MZt_i\right)\mathrm{\Delta }t_i\right]{\displaystyle \underset{j}{}}\mathrm{exp}\left[{\displaystyle \frac{I}{M^2}}2\left(M2kZ\left(t_jt_a\right)/2\right)\mathrm{\Delta }t_j\right]`$ (20)
$`=\mathrm{exp}\left[{\displaystyle _{t=0}^{t=t_a}}{\displaystyle \frac{I}{M^2}}2\left(MZt\right)𝑑t{\displaystyle _{t=0}^{t=t_b}}{\displaystyle \frac{I}{M^2}}2\left(M2kZt/2\right)𝑑t\right]`$ (21)
$`=\mathrm{exp}\left[{\displaystyle \frac{2I}{Z}}\right]\mathrm{exp}\left[{\displaystyle \frac{4I}{Z}}\left(\left({\displaystyle \frac{k}{M}}\right)^2\left({\displaystyle \frac{k}{M}}\right)\right)\right]`$ (22)
It is equally probable for the first nucleation to occur at any site along a column. We therefore have to average over all possible values of $`k`$ which are integers from zero to $`M/2`$. This gives

$`q`$ $`=q_k_k`$ (23)
$`=\mathrm{exp}\left[{\displaystyle \frac{2I}{Z}}\right]{\displaystyle \frac{2}{M}}{\displaystyle \underset{k=0}{\overset{k=M/2}{}}}\mathrm{exp}\left[{\displaystyle \frac{4I}{Z}}\left(\left({\displaystyle \frac{k}{M}}\right)^2\left({\displaystyle \frac{k}{M}}\right)\right)\right]`$ (24)
$`\mathrm{exp}\left[{\displaystyle \frac{2I}{Z}}\right]\left(2{\displaystyle _0^{1/2}}\mathrm{exp}\left[{\displaystyle \frac{4I}{Z}}\left(x^2x\right)\right]𝑑x\right)`$ (25)
$`=\mathrm{exp}\left[{\displaystyle \frac{I}{Z}}\right]\left({\displaystyle \frac{Z}{I}}\right)^{\frac{1}{2}}{\displaystyle \frac{\pi ^{\frac{1}{2}}}{2}}\mathrm{erf}\left[\left({\displaystyle \frac{I}{Z}}\right)^{\frac{1}{2}}\right]`$ (26)
Thus we have a relation between the probability of a nucleation leading to a perfectly doubled step and the ratio of the nucleation and zippering rates. It is to be noted that to preserve invariance under rescaling time, $`q`$ can only depend on the ratio of the rates and not on their absolute magnitude. Happily, equation 26 respects this invariance.

We now return to the question of when the approximation of considering only order-one defects is valid. To do this, we compute the value of the mean free path of a successful nucleation, defined earlier, explicitly. We first compute the probability that the doubled step length on one side of the point of nucleation exceeds $`l_0`$. At any time $`t_i`$ after the nucleation event the probability that the doubling step does not get stopped by doubling events in its path in the next time step ($`\mathrm{\Delta }t`$) is given by

$`P(i)`$ $`=(1{\displaystyle \frac{I}{M^2}}\mathrm{\Delta }t)^{6(l_0Zt_i/2)}`$ (27)
$`\mathrm{exp}\left[{\displaystyle \frac{I}{M^2}}6\left(l_0Zt_i/2\right)\mathrm{\Delta }t\right]`$ (28)
Here we take the probability of not stopping the zippering end of the doubling step in the next $`\mathrm{\Delta }t`$ of time to be the probability of having no nucleation in time $`\mathrm{\Delta }t`$ at any site raised to the power of the number of sites where such a nucleation would lead to stoppage (see fig. 3). Now the total probability is simply the product of the $`P_i`$’s which can be written as the exponential of an integral yielding

$$P(l>l_0)=\mathrm{exp}\left[\frac{6I}{Z}\left(\frac{l_0}{M}\right)^2\right]$$
(29)
Knowing this probability distribution we can calculate the mean length $`l`$, which is what we defined as the mean free path. The mean free path is thus

$$l=2_0^{\mathrm{}}\frac{dP}{dl}l𝑑l=M(\frac{4\pi }{6})^{\frac{1}{2}}(\frac{Z}{I})^{\frac{1}{2}}$$
(30)
Using the explicit formula for $`l`$ in terms of $`I/Z`$ above, the condition for neglecting higher order defects reduces to $`I/Z4\pi /62.09`$. As noted before for most realistic experimental situations this situation is easily satisfied. Simulation results presented later support our assumption.

Now, the value of $`q`$ derived above neglects the influence of nucleations other than the ones that can frustrate the initial zippering double step. For example a nucleation directly below and aligned with the original growing double step will block sites where nucleations could have frustrated the original growing double step. This is also true for nucleations on columns on either side of the original doubling step. In general a nucleation occuring many columns away may still influence the probability of the original nucleation forming a perfectly doubled step. Intuitively we would expect that the further such a column is from the original nucleation, the less its influence will be. Indeed for a nucleation occuring $`j`$ columns away the probablity that its effect will propagate to the column where the original nucleation took place will go as $`(I/Z)^j`$. This is because, for this to happen, we need $`j`$ nucleations (for each intervening column), each of which will occur roughly with a probability proportional to $`I/Z`$. Thus for small enough values of $`I/Z`$ we may neglect the effect of columns that are further away. However to be sure that this is not a big effect we need to ascertain the effect of nucleations on columns that are closest to the original doubling step. To do this, we need to take into account the probability that a site at which a nucleation could lead to frustration may not be available for occupation. Thus equation 16 will read

$$P_a(i)=\left(1\frac{I}{M^2}u\mathrm{\Delta }t\right)^{2(MZt_i)}$$
(31)
The extra factor $`u`$ reflects the probability that the site in question is available for occupation. $`u`$ may be roughly related in a “mean field” sense to the average fraction of unoccupied sites at that time. As an approximation we take this fraction to be $`P_1`$ for the case with an infinite zippering rate. Then going through the above analysis will yield a “corrected” value of $`q`$. We find that $`q`$ goes up by a factor which is about $`6.2\%`$ when $`q0.5`$ and less than $`0.1\%`$ when $`q0.9`$. Thus we find that neglecting these effects does not alter our results by much.

It is to be noted that when the only structures present were perfectly doubled steps ($`Z=\mathrm{}`$), the mapping to the RSA problem was exact. Now we have two kinds of entities. The doubled steps still cannot be overlapped and are put down randomly. They are still amenable to RSA analysis. However the frustrated dead ends can become defects of order two (fig.2) when the sections of them that are still single steps merge with a neighboring step if available. If this occurs during the process when there are still pairs of single steps that can form perfectly doubled steps, it will affect the dynamics and hence the asymptotic fraction of different species. It is this process that we neglect as a first approximation. Later simulation results show that this is a reasonable assumption.

We now consider how the competition parameter $`q`$ is altered when the surrounding lattice is not empty as discussed above. The value of $`q`$ does depend on the environment in which the nucleation occurs. We can imagine three possible scenarios. (1) Columns on either side of the freshly nucleated double step are already occupied (doubled). In this case $`q=1`$, since this nucleation cannot be frustrated. (2) Columns on both sides are empty (single). In this case we may use the result for the empty lattice, since for low enough $`I/Z`$, as we argued before, the state of columns further away will not matter much. (3) One side of the freshly nucleated double step is occupied. The correct value to be used here will be $`q^{1/2}`$. The relative probabilities of these scenarios occuring will evolve as a function of time. In order to account for this we ought to use the more general treatment, where $`q`$ can be an arbitrary function of time, presented in the previous section. However since most of the defects form in the early stages, we anticipate that the asymptotic fraction of defects will not be altered significantly if we use a constant value of $`q`$, evaluated for the empty lattice. Our simulation results confirm this view. The dynamics will however will be sensitive to changes in $`q`$ and this will be addressed in the section on time dependence. For now we take $`q`$ to be a fixed constant throughout the process.

We can now view the process as a RSA of a binary mixture of dimers and trimers on a 1-D lattice. A dimer adsorbs onto the lattice with a probability $`q`$ and a trimer with a probability $`1q`$. If $`k_0`$ is the overall attempt rate at which nucleations are tried on the 1-D lattice then the dimers have an attempt rate $`k=k_0q`$ and the trimers have an attempt rate $`k^{}=k_0(1q)`$. We now use the results derived for the process on an infinite 1-D lattice with dimers attempting to adsorb at a rate $`k`$ and trimers at a rate $`k^{}`$ (as in previous section). Using the fact that here $`k`$ and $`k^{}`$ are constants eq.12 yields

$$P_2=\mathrm{exp}\left[kt+2e^{(k+k^{})t}+\frac{k^{}}{k+k^{}}e^{2(k+k^{})t}(2+\frac{k^{}}{k+k^{}})\right]$$
(32)
and hence from (10) an explicit solution for all $`P_n`$ for $`n2`$. For $`n=1`$ we have

$$\frac{dP_1}{dt}=2kP_23k^{}P_3$$
(33)
which upon integration gives

$$1P_1(t=\mathrm{})=_0^{\mathrm{}}(2kP_2+3k^{}P_3)𝑑t$$
(34)
$`P_1(t=\mathrm{})`$ is simply the fraction of space occupied by isolated dead ends at asymptotic coverage. The two terms on the right are simply the fraction of space occupied by the dimers and trimers or double steps and frustrated dead ends respectively. Figure 4 shows a plot of the fraction of various species as a function of $`q`$. This is the only parameter in the problem as the asymptotic coverages are clearly independent of the overall rate $`k_0`$. Thus we have demonstrated that both the nature and number of defects in the final state depend only on the dimensionless parameter $`q`$. It is to be noted that the isolated single step population (not shown) does not change much ($`813.5\%`$) with $`q`$ in contrast to double steps and frustrated dead ends. This is in qualitative agreement with experimental results . It is also to be noted that when $`q0.58`$ , the fraction of width occupied by the defects exceeds that occupied by perfectly doubled steps. This characterization can be used to infer the ratio $`I/Z`$ by simply looking at the number of defects in the final structure. One thus gains information about the dynamics of the process from the final state.

### E  Scaling of the fraction of defects

A point of interest is the case where $`ZI`$. Here the nucleations are the rate limiting step and the zippering occurs almost instantaneously. In this case $`k^{}0`$ and we retrieve the $`Z=\mathrm{}`$ case where we can explicitly solve for $`P_1`$ yielding $`P_1(t=\mathrm{})=e^2`$. Thus even in this situation $`13.5\%`$ of the steps remain as isolated step defects.

In the limit of $`q1`$ the mapping to the RSA problem becomes exact. We now consider the scaling of the number of frustrated dead ends with $`ϵ1q`$ in this limit. The fraction of frustrated dead ends (defects of order one) is given by

$`p_{fr}`$ $`={\displaystyle _0^{\mathrm{}}}k^{}P_3𝑑t`$ (35)
$`={\displaystyle _0^{\mathrm{}}}k_0(1q)P_3𝑑t`$ (36)
$`=k_0ϵ{\displaystyle _0^{\mathrm{}}}\mathrm{exp}[k_0t]P_2𝑑t`$ (37)
$`=k_0ϵ{\displaystyle _0^{\mathrm{}}}\mathrm{exp}[k_0t]\mathrm{exp}\left[kt+2e^{(k+k^{})t}+{\displaystyle \frac{k^{}}{k+k^{}}}e^{2(k+k^{})t}(2+{\displaystyle \frac{k^{}}{k+k^{}}})\right]𝑑t`$ (38)
Here $`k=k_0(1ϵ)`$ and $`k^{}=k_0ϵ`$. Using these in the above expression and retaining terms to lowest order in $`ϵ`$ we obtain

$`p_{fr}`$ $`=k_0ϵe^2{\displaystyle _0^{\mathrm{}}}\mathrm{exp}[2k_0t+2e^{k_0t}]𝑑t`$ (39)
$`=ϵe^2{\displaystyle _0^{\mathrm{}}}\mathrm{exp}[2x+2e^x]𝑑x`$ (40)
$`=0.284\mathrm{}ϵ`$ (41)
Thus for small $`ϵ`$ the fraction of frustrated dead ends rises linearly with $`ϵ`$ with a slope of $`0.284`$. Figure 5 shows a plot of values of $`p_{fr}`$ obtained from the simulations described in the section.III versus $`ϵ`$. The error bars on the individual data points are about $`5\%`$. The line plotted is a best fit line to the points and yields a slope of $`0.28\pm 0.01`$ and an intercept of $`0.0000\pm 0.0002`$. This agrees very well with our prediction and shows that $`p_{fr}`$ indeed rises linearly with $`ϵ`$ with a slope of $`0.28`$. The observed number of frustrated dead ends thus gives us explicit information about the competition parameter $`q`$ and hence the experimental rates.

### F Accounting for nucleations outside the field of view

In the above analysis we assumed that all doubling occurred as a result of nucleations that occurred within the region of observation. Clearly this need not be the case. Nucleations that occur outside the region of observation can lead to doubled steps within this region. In a typical experimental situation for example one would be most likely to examine some subsection of the sample and take that subsection as being representative. We thus need to account for unobserved nucleations in order to make contact with experiment.

Most of the analysis done before still holds for this case. Nucleations occurring outside the field of view will increase the overall attempt rate (since there will be doubled steps formed by nucleations occurring outside and zippering in). They will also make it more probable for a given nucleation to be frustrated (since nucleations occurring outside can also frustrate doubling steps within the field of view). If we are interested only in the asymptotic fraction of defects, we do not need to consider changes in the overall attempt rate. The only difference will arise in computing the probability that a given attempt at a doubled step succeeds without being frustrated i.e. our competition parameter $`q`$. We take the region of observation to be an $`M\times M`$ lattice embedded in a larger lattice which is $`3M\times 3M`$. The choice is simply made based on convenience and for ease of comparison with simulations. First we recall the concept of a mean free path for a zippering double step. We defined this to be the average length to which a zippering double step can grow from the nucleation point without being hindered by a nucleation in its path. Taking into account the probability per unit time of a nucleation occuring in the path and the zippering speed it was shown that the probability of a zippering double step growing to a length greater than $`l_0`$ is

$$p(l>l_0)=\mathrm{exp}\left[\frac{6I}{Z}(\frac{l_0}{M})^2\right]$$
(42)
where $`I`$ is the nucleation rate over an $`M\times M`$ area. Knowing this probability distribution we can calculate the mean length $`l`$ which is what we defined as the mean free path. The mean free path is thus

$$l=M\left(\frac{4\pi }{6}\right)^{\frac{1}{2}}\left(\frac{Z}{I}\right)^{\frac{1}{2}}$$
(43)
Now we assume that the only nucleations that will have an effect on the region of observation occur either in this region or $`l`$ above or below this region. This is because a zipper originating from a nucleation farther away is likely to be cut off by nucleations in its path. As before we consider the scenario at a time $`t`$ after a nucleation event inside the region of interest, $`k`$ lattice constants away from the nearest edge of the $`M\times M`$ lattice on an otherwise empty lattice. The probability that this nucleation leads to a perfectly doubled step may be derived in a manner analogous to the way we derived equation (22). There are two factors contributing to this probability. First there is the probability of being frustrated by nucleations inside the field of view. This is exactly the same as before. We denote this as $`P_{in}`$, which is given by

$$P_{in}=\mathrm{exp}\left[\frac{2I}{Z}\right]\mathrm{exp}\left[\frac{4I}{Z}\left((\frac{k}{M})^2(\frac{k}{M})\right)\right]$$
(44)
This follows from eq.22. The second factor which we now consider, is to account for nucleations occurring outside the field of view. Now the probability at a time $`t_i<t_a`$ past a nucleation that the doubling steps do not get frustrated in the next $`\mathrm{\Delta }t`$ of time is given by

$$P_{out}^1(i)=\left(1\frac{I}{M^2}lP_2p\mathrm{\Delta }t\right)^4$$
(45)
Here $`t_a=2k/Z`$ as before. $`p`$ refers to the average probability that a nucleation within a mean free path distance of the horizontal edge of the field of view, zippers to the edge without being cut off. This is simply the average of the probability given by eq.42 over this region.

$$p=\left(\frac{Z}{6I}\right)^{1/2}\frac{M}{l}\frac{\pi ^{1/2}}{2}\mathrm{erf}\left[\left(\frac{Z}{6I}\right)^{1/2}\frac{l}{M}\right]$$
(46)
$`P_2`$ accounts for the probability that a nucleation is indeed possible at the site in question. We simply choose for $`P_2`$ the solution for the infinite zippering rate case (eqs.8 and 4). The factor of $`4`$ comes from the fact that there are four columns along which a nucleation from outside can zipper in to frustrate the original nucleation (see fig.3). We can write down a similar expression for times $`t_a<t_i<t_a+t_b`$ where $`t_b=2(M2k)/Z`$.

$$P_{out}^2(i)=\left(1\frac{I}{M^2}lP_2p\mathrm{\Delta }t\right)^2$$
(47)
The change here is in the exponent which changes from $`4`$ to $`2`$, since once one end has reached the edge, there are only two columns left along which a nucleation from outside can zipper in to cause frustration. We now take the product $`P_{out}^1P_{out}^2`$ and integrate over time to get

$$P_{out}=\mathrm{exp}\left[\frac{4I}{M^2}lp_0^{t_a}P_2𝑑t\right]\mathrm{exp}\left[\frac{2I}{M^2}lp_0^{t_b}P_2𝑑t\right]$$
(48)
We similarly consider the probability that a nucleation event that occurs outside the region (within $`l`$ of the edge of the region of interest) results in a perfectly doubled step.

$$P^0=\mathrm{exp}\left[\frac{2I}{Z}\right]\mathrm{exp}\left[\frac{2I}{M^2}lp_0^{2M/Z}P_2𝑑t\right]$$
(49)
This comes from putting $`k=0`$ in the product $`P_{in}P_{out}`$. This has to be weighted by the probability that the particular nucleation results in a zipper that makes it to the edge. This probability as calculated before (eq.42) is

$$p(j)=\mathrm{exp}[\frac{6I}{Z}(\frac{j}{M})^2]$$
(50)
Now we simply average the probability of getting a perfectly doubled step over all positions (both inside and outside) with the appropriate weights following the steps to get eq.26. It is to be noted that if the distance from the edge of the field of view to the edge of the outer boundary is less than the mean free path, then $`l`$ in the above expressions is to be replaced by this distance. The integrals cannot be performed to yield a closed form answer. These however can be numerically evaluated for specified values of $`I/Z`$. The dependence of the fraction of species on $`q`$ remains the same as before. Only the relation between $`q`$ and $`I/Z`$ has changed. Figure 6 shows a plot of the fraction of various species as a function of $`q`$. It is to be noted that, for the same value of $`I/Z`$, an open subsystem will have a smaller value of $`q`$ and hence a larger number of frustrated dead ends than a closed system of the same size (see fig.7). This is what one would intuitively expect.

One can use this analysis to infer the number and nature of defects in a larger sample simply by looking at a small patch and inferring the value of $`I/Z`$. However care must be taken if the calculated value of $`I/Z`$ for the larger sample exceeds about 0.5. One must then do an extended analysis incorporating a finite number of higher order defects dictated by the value of $`I/Z`$. It is to be noted that this treatment contains several ad hoc approximations and should only be taken as a rough estimate and a proposed methodology.

### G Time Dependence

Until now we have been looking at the asymptotic ($`t\mathrm{}`$) limit of the surface morphology. In this non-equilibrium problem however the final morphology is dictated by the dynamic evolution and hence it is interesting to look at this evolution. Experimentally too there has been recently much progress in studying the time evolution of the step doubling process .

We first introduce an order parameter $`\psi `$ which we define to be the fraction of sites that have undergone doubling. A completely empty matrix in which all steps are single corresponds to $`\psi =0`$ and a completely full state in which all sites are doubled corresponds to $`\psi =1`$. At the beginning ($`t=0`$) we start with a situation where all the steps are single ($`\psi =0`$). Now consider the situation after a time $`t`$. We define the average time it takes for a perfectly doubled step to form to be $`t_2^{}=3M/2Z`$ . We assume it takes roughly half the time for a frustrated dead end to form and define $`t_3^{}=3M/4Z`$. We make these approximate estimates since we would just like to give a qualitative sense of the time dependence. Now all double steps initiated before time $`tt_2^{}`$ and all frustrated dead ends initiated before time $`tt_3^{}`$ have formed completely. Entities initiated within this interval have formed partly. So we have

$$\psi (t)=_0^{tt_2^{}}2kP_2𝑑t^{}+_0^{tt_3^{}}2k^{}P_3𝑑t^{}+_{tt_2^{}}^t2k^{}P_2\frac{tt^{}}{t_2^{}}𝑑t^{}+_{tt_3^{}}^t2k^{}P_3\frac{tt^{}}{t_3^{}}𝑑t^{}$$
(51)
The first two terms account for the completely formed (completed double steps and frustrated dead ends) structures. The third and fourth terms account for the structures that are partly formed. The factor of two in all the terms comes from the fact that each doubled step occupies two columns. The frustrated dead ends also effectively occupy two columns (in terms of area) though they span three columns. Since we have explicit solutions for $`P_2`$ and $`P_3`$ as functions of time we can compute $`\psi (t)`$. The only parameter we have not yet evaluated is the overall attempt rate $`k_0`$. We may think of each doubled step as being caused by one nucleation and each frustrated dead end being caused by two. Then the attempt rate of dimers plus twice the attempt rate of triplets ought to be equal to the nucleation rate per column.

$`k+2k^{}`$ $`=k_0q+2k_0(1q)`$ (52)
$`=k_0(2q)={\displaystyle \frac{I}{M}}`$ (53)
which yields

$$k_0=\frac{I}{M(2q)}$$
(54)
Having evaluated $`k_0`$ we can now compute $`\psi (t)`$ explicitly in terms of $`I`$, $`Z`$ and $`M`$. Figure 8 shows a plot of the computed $`\psi (t)`$ (dashed line) as a function of time for two different values of $`I/Z`$ (0.05 and 0.1). $`Z=2`$ in both cases. The difference between the two curves shows that the dynamics is quite sensitive to the parameters. Thus combining the information about the defects in the asymptotic structure and a measurement of the time dependence of $`\psi (t)`$ will allow us to uniquely determine both the nucleation and zippering rates. The mismatch between the analytical and simulation curves at late times was anticipated before and comes from the assumption of a constant $`q`$. To fix this, we use the solution for the case with the time dependent competition parameter, $`q(t)`$. To do this, we need to compute $`q(t)`$. Now, the value of $`q`$ depends on where a particular nucleation event takes place. As mentioned before, if the nucleation takes place at a site which belongs to a set of two empty sites with doubled steps on either side, the value of $`q`$ is unity since this doubling step cannot be frustrated. This situation would occur with a probability $`1P_3`$. This includes the probability of picking isolated single steps where nucleations are not possible, resulting in the attempt being rejected. As a first approximation we assume that nucleation attempts at all other places (with probability $`P_3`$) have the value of $`q`$ computed for an empty lattice, $`q_0`$. In principle we can systematically refine this approximation by considering sites adjacent to a double step but belonging to a large set of consecutive empty sites having a different value of $`q`$ and so on. However we find that the first level of approximation is sufficient for our purposes. Thus we take the competition parameter to have a time dependent value

$$q(t)=q_0\times (P_3)+1\times (1P_3)$$
(55)
We now solve the set of equations (12), (55) and (54) self-consistently by an iteration procedure starting with the solution for the case with a constant competition parameter, $`q_0`$. The results after a couple of iterations are plotted in 8 as solid lines. One immediately sees that these agree with the simulation points much better at later times. Thus our treatment allows us to capture the time evolution of the surface morphology fairly accurately.

## III Simulation

We now describe the simulation that produced the data in figures 2–5. This simulation uses the coarse-grained representation of figure 1 but makes none of the assumptions leading to the curves in figures 2–5. It thus serves as a test of our RSA approximations. We use an $`M\times M`$ matrix to mimic a square section of the sample. Every column of the matrix is regarded as a step. We have two experimental parameters that we may use: the nucleation rate $`I`$ and the zippering rate $`Z`$. A typical simulation cycle is as follows:
(1)A randomly chosen site of the matrix is addressed.
(2) If a chosen site is unoccupied and its neighbor to the right is also unoccupied these two sites are allowed to combine to form a nucleus with a probability $`p=I/M^2Z`$. This takes care of the relative rates of nucleation and zippering. Now these two sites are considered occupied.
(3) Steps (1) and (2) are repeated making sure sites are not addressed twice until all sites of the matrix have been addressed.
(4) All steps that have previously initated doubling are allowed to grow by one lattice unit at each free end, if possible.
(5) Steps (1)-(4) are repeated until no new nucleations are possible and the surface is comprised only of perfectly doubled steps, frustrated dead ends and isolated single steps.
(5) The results are averaged over hundreds of runs for different values of the ratio $`I/Z`$.

### A Final State

The size of the matrix used was $`M=60`$ since the STM experiment described in  has a field of view roughly 60 terraces wide and 60 terraces tall. In the range of parameter values we looked at the number of defects that were not simple frustrated dead ends were few ($`15\%`$ of the defects for $`q=0.5`$ and decreasing with increasing $`q`$), thus justifying the rationale for our theoretical assumption. When these were encountered they were decomposed into constituent dead ends and counted as that many effective frustrated dead ends. For example an order two defect was counted as one frustrated dead end and one isolated step. Figure 4 plots the results of the simulation for various values of $`I/Z`$. We see very good agreement between the simulation and values predicted by theory for small $`I/Z`$. We also see that the theory begins to break down for large values of $`I/Z`$ ($`>0.46`$). It is to be noted that the largest number of perfectly doubled steps occurs in the limit of $`ZI`$ and is about $`43.75\%`$. This is consistent with our prediction for the $`Z=\mathrm{}`$ case.

We also consider the case where the region of interest is part of a larger region. We utilize the same $`M=60`$ matrix and we now count the defects and doubled steps in the central $`20\times 20`$ submatrix. Figure 6 plots the results of the simulation for various values of $`I/Z`$. The agreement between the theoretical curve and the simulation values appear to be quite good in this case too.

### B Time dependence

We also look at the evolution of the order parameter $`\psi `$ during a simulation run. The simulation is done on a $`60\times 60`$ matrix as before. The fraction of sites that are occupied ( doubled ) is registered after every 10 simulation timesteps. This data is recorded for hundreds of whole simulation runs. For each block of 10 timesteps we then record the average $`\psi `$ over all the runs. Figure 8 shows a plot of the averaged evolution of the order parameter as a function of simulation time for two different values of $`I/Z`$. We see that the simulation data and the theoretical curves agree quite well. It is to be noted that there are no adjustable parameters.

Thus overall the simulation results are in agreement with the theory and the theory effectively captures both the dynamics and the details of the asymptotic surface morphology.

## IV Discussion of Results

We now compare our results to experimental data so as to be able draw some physical conclusions. In the experiments by Wang et al it was noted that under certain optimal conditions, a 100 nm by 100 nm section of the sample exhibited 5-6 frustrated dead ends after structural evolution had reached an asymptotic stage. The step zippering rate was measured to be 3.7 Å$`s^1`$. The case to which this data ought to be compared is the one where the region of interest is embedded in a larger region. From figure 6 we immediately see that to get 5-6 frustrated dead ends in a $`60\times 60`$ matrix we require $`q0.7`$. This gives us a value for the ratio $`I/Z0.12`$. Knowing the experimentally measured zippering rate we can also deduce the true nucleation rate. In our model we have $`Z=2`$ measured in units of step width per simulation timestep. The step width is about 1.65 nm which tells us that each simulation timestep corresponds to $`2\times 1.65/0.379`$ seconds. Thus the true nucleation rate in this case would be $`0.12/9=0.0133`$ nucleations per second over the 100 nm by 100 nm section of the sample. Our analysis hence helps pin down the true experimental parameters simply by looking at the defects in the asymptotic stage.

Our analysis of the dynamics also gives us more useful insights. In particular we notice that $`P_3\mathrm{exp}(kt)P_2`$ (from eq.(10)). This tells us that the rate of defect formation drops exponentially faster than the rate at which perfectly doubled steps form. Often one wishes to minimize the number of defects. The way to do that would be to have a very low nucleation rate (for a given zippering rate ). However then reaching the final state would take a very long time. Since we anticipate that most of the defects will be formed in the intial stages we could start with a low nucleation rate and after some time jump to a much higher rate. This would mean reaching the final state much faster with only a small increase in the number of defects. As an example we ran a simulation with $`I/Z=0.05`$ on a $`M=60`$ lattice. The number of defects was roughly one and it took 3600 timesteps to go to completion. A run where we started with the same value of $`I/Z`$ and then switched to a value 20 times higher ($`I/Z=1`$) after 500 timesteps yielded two defects and took only 700 timesteps to complete. In contrast if we run the simulation for $`I/Z=1`$ from the beginning we get approximately 12 defects. Thus we gained a factor of 5 in time for a minor increase in the number of defects. One can also imagine trying different time dependent protocols to optimize the number of defects and the time.

Our prediction for the dynamic evolution of the order parameter (figure 8) is qualitatively similar to experimental data by Niu et al . The authors use a phenomenological approach to fit their data using second order rate kinetics. Though the fit is good the analysis neglects that the fact that only neighboring steps can double. Another approach by Khare et al  analyzes the dynamics in terms of first passage times of random walkers using a fit with three adjustable parameters. However as the authors note, they do not take into account the formation of defects like the isolated steps and frustrated dead ends. Our analysis allows us to inspect the dynamics with no adjustable parameters if we first extract the relevant parameters from an inspection of the asymptotic structure. It also takes into account the formation of defects and their effect on the subsequent dynamics. This cannot be ignored for a manifestly non-equilibrium problem such as this.

There are however several details which we have ignored in this analysis. Firstly it was noticed  that zippering occurs much more slowly when the steps are surrounded by already doubled steps. Secondly we have not taken into account correlations between neighboring zippers. Another avenue of interest would be to integrate the time distribution of nucleation events postulated by Khare et al  with our RSA analysis. One could also incorporate higher order defects by a straightforward elaboration of our treatment. Thus it appears that our RSA approach will be applicable to a a range of such propagating surface reconstruction processes. Though we know of only one such process at the moment, many others are sure to emerge as atomic scale knowledge of adsorption on solid surfaces improves.

## V Conclusion

We have shown here how emergent features of the novel step-doubling process can be quantitively understood. Our approximation of the process as a form of random sequential absorption leads to successful predictions in regions of experimental interest. The approximation permits simple analysis, yet it shows that naive analysis based on equilibrium statistics is misleading. The inadequacy of an equilibrium treatment is further apparent in the time-dependence of our results. Changing the growth conditions over time can have a striking effect on the final state.

We have focussed on predicting the incidence of a particular type of defect: the frustrated dead end. But the method gives a way of understanding higher-order composite defects as well. Experimental mastery of propagating surface self-organization such as step doubling will improve over time. Along with this improvement, we expect stochastic models like the present one to be valuable guides in achieving desired structures.

## VI Acknowledgements

The authors would like to thank V. Belyi, Y. Wang and S.J. Sibener for useful discussions. AG would also like to thank R. Bao, L. Tseng and E. Yuzbashyan for engaging conversations on the topic. This work was supported by the National Science Foundation via its MRSEC program under award number DMR 0213745.


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# 1 Eigenvalues and wave functions of equation (17) for four values of 𝛼. Normalizations (not including the (2𝜋)^{-{1/2}} from the ϕ dependence) are in brackets proceeding the functions. Terms not shown are at least an order of magnitude smaller than those listed. There are no negative parity states with 𝛽<0.

Curvature induced toroidal bound states

Mario Encinosa and Lonnie Mott

Department of Physics

Florida A & M University

Tallahassee, Florida 32307

## Abstract

Curvature induced bound state ($`E<0`$) eigenvalues and eigenfunctions for a particle constrained to move on the surface of a torus are calculated. A limit on the number of bound states a torus with minor radius $`a`$ and major radius $`R`$ can support is obtained. A condition for mapping constrained particle wave functions on the torus into free particle wave functions is established. Pacs number(s): 03.65Ge, 68.65.-k

$`\mathrm{𝟏}.\mathrm{𝐈𝐧𝐭𝐫𝐨𝐝𝐮𝐜𝐭𝐢𝐨𝐧}`$. The physics of nanostructures  and quantum waveguides \[3-7\] may make questions concerning curved surfaces in quantum theory increasingly relevant to device modelling. Many workers have investigated with varying levels of formal machinery the existence of bound states of quantum systems on curved strips, tubes and hypervolumes \[8-12\]. The common thread through much of the work described in \[8-12\] is the existence of an attractive potential that appears in the Schrodinger equation as a consequence of constraining a particle from higher to lower dimensional manifolds. (In the majority of work the dimensionality is reduced from three to two, but see  for the generalization to other cases.) This potential, called here the curvature potential $`V_C`$, has been shown sufficient to cause bound states in model systems. In this work $`V_C`$ for a particle constrained to the surface of a torus is derived and bound state surface toroidal wavefunctions (STWs) are calculated.

This brief report is organized as follows: in section 2 the method by which $`V_C`$ is derived is concisely described for a symmetric but non-trivial geometry. The method is then applied to the torus. In section 3 a brief description of the procedure used to solve the Hamiltonian found in section 2 is given and some low-lying bound state eigenvalues and STWs shown. Conclusions appear in section 4.

$`\mathrm{𝟐}.\mathrm{𝐃𝐞𝐫𝐢𝐯𝐚𝐭𝐢𝐨𝐧}\mathrm{𝐨𝐟}𝐕_𝐂`$.

In the interest of clarity the derivation of $`V_C`$ will be performed for a cylindrically symmetric surface. The extension to the general case is straightforward and the salient points still obtain.

Let $`𝐞_\rho ,𝐞_\varphi ,𝐞_z`$ be standard cylindrical coordinate system unit vectors. A cylindrically symmetric surface may be described by the Monge form

$$𝐫(\rho ,\varphi )=\rho 𝐞_\rho +S(\rho )𝐞_z.$$
$`(1)`$
$`S(\rho )`$ gives the shape of the surface. Points near the surface $`S(\rho )`$ may be described by

$$𝐱(\rho ,\varphi ,q)=𝐫(\rho ,\varphi )+q𝐞_n$$
$`(2)`$
with $`𝐞_n`$ everywhere normal to the surface. The metric near the surface $`S`$ is

$$ds^2=Z^2\left[1\frac{qS_{\rho \rho }}{Z^3}\right]^2d\rho ^2+\rho ^2\left[1\frac{qS_\rho }{\rho ^2Z}\right]^2d\varphi ^2+dq^2$$
$`(3)`$
$$Z^2[1+qk_1]^2d\rho ^2+\rho ^2[1+qk_2]^2d\varphi ^2+dq^2$$
$`(4)`$
with subscripts indicating differentiation and $`Z=\sqrt{1+S_\rho ^2}`$. The Laplacian can be found straightforwardly from

$$^2=g^{\frac{1}{2}}\frac{}{q^i}\left[g^{\frac{1}{2}}g^{ij}\frac{}{q^j}\right],$$
$`(5)`$
but there is no advantage to writing the the Laplacian explicitly until the constraint that places the particle on the surface is effected.

Consider a situation where a large confining potential everywhere normal to $`S`$ acts to restrict the particle to $`S`$. This potential, called $`V_n(q)`$ here, could take a hard wall or oscillator form, but however chosen it causes $`q0`$. In this limit the wave function is expected to decouple into surface and normal parts, or in the language of , into $`\mathrm{`}\mathrm{`}`$fast” and $`\mathrm{`}\mathrm{`}`$slow” functions

$$\mathrm{\Psi }(\rho ,\varphi ,q)\chi _s(\rho ,\varphi )\chi _n(q).$$
$`(6)`$
Conservation of the norm in the decoupled limit implies

$$|\mathrm{\Psi }|^2WdSdq=|\chi _s|^2|\chi _n|^2dSdq$$
$`(7)`$
where $`W=1+2qH+q^2K`$ and $`dS`$ the surface measure. $`H,K`$ are the mean and Gaussian curvatures given by

$$H=\frac{1}{2}(k_1+k_2),$$
$`(8)`$
$$K=k_1k_2.$$
$`(9)`$
Write

$$\mathrm{\Psi }=\frac{\chi _s\chi _n}{\sqrt{W}}$$
$`(10)`$
and insert the right hand side of equation (10) into the time independent Schrodinger equation. Performing the differentiations and taking $`q0`$ gives the pair of equations

$$\frac{1}{2}\left[\frac{1}{Z^2}\frac{^2}{\rho ^2}+\frac{1}{Z\rho }\frac{}{\rho }\frac{Z_\rho }{Z^3}\frac{}{\rho }+\frac{1}{\rho ^2}\frac{^2}{\varphi ^2}+(H^2K)\right]\chi _s=E_s\chi _s$$
$`(11)`$
$$\frac{1}{2}\frac{^2\chi _n}{q^2}+V_n(q)\chi _n=E_n\chi _n.$$
$`(12)`$
The curvature potential $`V_C`$ is

$$V_C=\frac{1}{2}[H^2K].$$
$`(13)`$
The surface given by equation (1) was chosen to illustrate that there are modifications to the Laplacian (aside from the appearance of $`V_C`$) even for surfaces possessing symmetry. In  it was shown that kinetic energy modifications for some parameterizations of $`S(\rho )`$ can be small, but it is easy to conceive of cases where the contrary would be true.

Now apply the above procedure to the torus. Let $`F=R+a\mathrm{cos}\theta `$. Points near the surface of the torus may be parameterized as

$$𝐱(\theta ,\varphi ,q)=F𝐞_\rho +a\mathrm{sin}\theta 𝐞_z+q𝐞_n.$$
$`(14)`$
Proceeding as above gives the constraint and curvature modified Hamiltonian

$$H=\frac{1}{2}\left[\frac{1}{a^2}\frac{^2}{\theta ^2}\frac{\mathrm{sin}\theta }{aF}\frac{}{\theta }+\frac{1}{F^2}\frac{^2}{\varphi ^2}+\frac{R^2}{a^2}\frac{1}{4F^2}\right]$$
$`(15)`$
$$=H_0\frac{R^2}{a^2}\frac{1}{8F^2}H_0+V_C.$$
$`(16)`$
In equation (16), $`H_0`$ is identical to $`\frac{1}{2}^2`$ derived from eq. (14) with $`q=0`$; it is the Hamiltonian for particle on a toroidal surface subject to no other potential  (it proves convenient to refer to the zero potential case as the free system). In contrast to the operator that appears in equation (11), no surface dependent prefactors, i.e. $`Z(\rho )`$ or additional terms modifying $`H_0`$ are present. It is interesting to compare equation (15) to the corresponding operator for spherical and cylindrical surfaces; for those surfaces the constraint procedure gives a coordinate independent $`V_C`$ behaving as $`1/R^2`$  and again no modifications to $`H_0`$. This point will be discussed further in section 4. $`\mathrm{𝟑}.\mathrm{𝐒𝐨𝐥𝐮𝐭𝐢𝐨𝐧}\mathrm{𝐦𝐞𝐭𝐡𝐨𝐝};\mathrm{𝐫𝐞𝐬𝐮𝐥𝐭𝐬}`$. Setting $`\alpha =\frac{a}{R},`$ $`\beta =2Ea^2`$ and making the standard ansatz for the azimuthal eigenfunction $`\chi (\varphi )=exp[im\varphi ]`$ in equation (15) gives

$$\frac{^2\psi }{\theta ^2}\frac{\alpha \mathrm{sin}\theta }{[1+\alpha \mathrm{cos}\theta ]}\frac{\psi }{\theta }\frac{(m^2\alpha ^2\frac{1}{4})}{[1+\alpha \mathrm{cos}\theta ]^2}\psi +\beta \psi =0.$$
$`(17)`$
Equation (17) can be solved numerically, but it is convenient to have approximate analytic representations of its eigenfunctions. Recently a method was found for obtaining closed form solutions for zero energy states and for surface potentials $`V_S(\theta )`$ which satisfy an auxiliary condition derivable from $`H_0`$ . However, the $`V_S(\theta )=0`$ case is no more easily solved with the method given in  than the method employed below.

Solutions of equation (17) can be found by defining $`z=exp[i\theta ]`$ and writing

$$\psi (z)=\underset{n=\mathrm{}}{\overset{\mathrm{}}{}}c_nz^n.$$
$`(18)`$
The Hamiltonian given by equation (15) is invariant under $`\theta \theta `$, so the solutions of equation (17) can be split into odd and even parity eigenfunctions, yielding a series in sines for negative parity states and cosines for positive parity states. Computing the eigenvalues and eigenfunctions of equation (17) follows from a method given in detail in .

Table 1 shows eigenvalues and wave functions for $`\alpha =3/4,1/2,1/4,1/20`$ for those $`m`$ values which yield $`\beta <0`$ states (only three states are given for $`\alpha =1/20`$; there are nine total). No negative parity states appear in table 1. In table 2 wave functions for states corresponding to those in table 1 with $`V_C`$ shut off are given. As evidenced in table 2, the ground state $`m=0`$ wave function of $`H_0`$ for any $`\alpha `$ is a constant. A natural question is: Should the $`V_C0`$ ground state wave function be compared to the constant wave function or the lowest $`\beta 0`$ wave function? Here the constant wave function was chosen on the grounds that it is the state actually altered from its constant value by $`V_C`$.

$`\mathrm{𝟒}.\mathrm{𝐂𝐨𝐧𝐜𝐥𝐮𝐬𝐢𝐨𝐧𝐬}`$. In this brief report wave functions for bound states of a particle constrained to the surface of a torus were obtained for several values of $`\alpha =a/R`$. Constraint and curvature effects were shown to alter the angular dependence of the free particle STWs.

An interesting consequence of equation (17) is manifested by the results presented in table 1. For $`m0`$, $`\alpha =\frac{1}{2m}`$ provides a cutoff for the existence of bound states. It follows that there are no $`m0`$ bound states for $`\alpha >1/2`$. Additionally $`\alpha =1/2m`$ provides a series of magic radii for which an $`m0`$ state of the constrained system maps exactly into the $`m=0`$ state with the same $`n`$ and parity of the $`V_C=0`$ free STW.

In section 2 it was stated that the torus shares with the sphere the property that constraint adds only a curvature potential to the Hamiltonian, leaving $`^2`$ on the surface unchanged. This comparable behavior is likely a consequence of the torus being the most symmetric compact genus one surface that can be embedded in $`R^3`$. It would be interesting to learn if there are higher genus surfaces embedded in $`R^3`$ for which $`H=\frac{1}{2}^2`$ reduces to the lower dimensional operator $`H_0`$ plus a curvature potential upon imposing the condition given by equation (10). This question generalizes to $`M<N`$ dimensional surfaces embedded in $`R^N`$.

Acknowledgments

The authors would like to acknowledge useful discussions with Babak Etemadi. M.E. would like to thank Norman Melom for useful suggestions. Both authors received support from NASA grant NAG2-1439.

References

1. S. M. Reimann and M. Manninen, Rev. Mod. Phys. $`\mathrm{𝟕𝟒}`$, 1953 (2002). 2. D. Ferry and S. Goodnick, $`\mathrm{𝑇𝑟𝑎𝑛𝑠𝑝𝑜𝑟𝑡}\mathrm{𝑖𝑛}\mathrm{𝑛𝑎𝑛𝑜𝑠𝑡𝑟𝑢𝑐𝑡𝑢𝑟𝑒𝑠}`$, (Cambridge University Press, U.K., 1992). 3. P. Ouyang, V. Mohta and R. L. Jaffe, Ann. of Phys. $`\mathrm{𝟐𝟕𝟓}`$, 297 (1998). 4. I. Y. Popov, Phys. Lett. A $`\mathrm{𝟐𝟔𝟗}`$, 148 (2000). 5. S. Midgley, Aus. J. Phys $`\mathrm{𝟓𝟑}`$, 77 (2000). 6. J.T. Londergan, J.P. Carini, D.P. Murdock, $`\mathrm{𝐵𝑖𝑛𝑑𝑖𝑛𝑔}\mathrm{𝑎𝑛𝑑}\mathrm{𝑠𝑐𝑎𝑡𝑡𝑒𝑟𝑖𝑛𝑔}\mathrm{𝑖𝑛}\mathrm{𝑡𝑤𝑜}\mathrm{𝑑𝑖𝑚𝑒𝑛𝑠𝑖𝑜𝑛𝑎𝑙}`$ $`\mathrm{𝑠𝑦𝑠𝑡𝑒𝑚𝑠};\mathrm{𝑎𝑝𝑝𝑙𝑖𝑐𝑎𝑡𝑖𝑜𝑛𝑠}\mathrm{𝑡𝑜}\mathrm{𝑞𝑢𝑎𝑛𝑡𝑢𝑚}\mathrm{𝑤𝑖𝑟𝑒𝑠},\mathrm{𝑤𝑎𝑣𝑒𝑔𝑢𝑖𝑑𝑒𝑠},\mathrm{𝑎𝑛𝑑}\mathrm{𝑝ℎ𝑜𝑡𝑜𝑛𝑖𝑐}\mathrm{𝑐𝑟𝑦𝑠𝑡𝑎𝑙𝑠}`$, (Springer-Verlag Berlin, 1999). 7. J. Goldstone and R. L. Jaffe, Phys. Rev. B $`\mathrm{𝟒𝟓}`$, 14102 (1991). 8. I. J. Clark and A. J. Bracken, J. Phys. A $`\mathrm{𝟐𝟗}`$, 4527 (1996). 9. P. Duclos and P. Exner, $`\mathrm{𝑅𝑒𝑣𝑖𝑒𝑤𝑠}\mathrm{𝑖𝑛}\mathrm{𝑚𝑎𝑡ℎ𝑒𝑚𝑎𝑡𝑖𝑐𝑎𝑙}\mathrm{𝑝ℎ𝑦𝑠𝑖𝑐𝑠}`$, $`\mathrm{𝟕}`$, 73 (1995). 10. D. Krejcirik, J. Geom. Phys. $`\mathrm{𝟒𝟓}`$, 203 (2003). 11. P. C. Schuster and R. L. Jaffe, hep-th /0302216 12. R. C. T. da Costa, Phys. Rev. A $`\mathrm{𝟐𝟑}`$, 1982 (1981). 13. L.Kaplan, N.T. Maitra and E.J. Heller, Phys. Rev. A $`\mathrm{𝟓𝟔}`$, 2592 (1992). 14. R. C. T. da Costa, Phys. Rev. A $`\mathrm{𝟐𝟓}`$, 2893 (1982). 15. M. Encinosa and B. Etemadi, Physica B $`\mathrm{𝟐𝟔𝟔}`$, 361 (1998). 16. M. Encinosa and B. Etemadi, Phys. Rev. A $`\mathrm{𝟓𝟖}`$, 77 (1998). 17. M. Encinosa and B. Etemadi, quant-ph /0200501, and submitted to Found. Phys. Lett. 18. H. Jensen and H. Koppe, Ann. of Phys. $`\mathrm{𝟔𝟑}`$, 586 (1971). 19. A. Schulze-Halberg, Found. Phys. Lett. $`\mathrm{𝟏𝟓}`$, 585 (2002).


text:
# Point contact spectroscopy of the electron-doped cuprate superconductor Pr2-xCexCuO4: The dependence of conductance-voltage spectra on cerium doping, barrier strength and magnetic field

## I Introduction

Point contacts between a normal metal and a superconductor have been extensively employed to probe the quasiparticle states of superconductors near the Fermi energy. Point contact spectroscopy (PCS) experiments have also been done to investigate the pairing symmetry of superconductors and the presence or absence of nodes in the superconducting order parameter . In particular, in the hole doped copper oxide high Tc superconductors (HTSC), PCS and junction tunneling experiments have shown that the pairing symmetry is predominantly $`d`$-wave , strongly supporting the results of many other types of experiments . Some of the tunneling experiments have even suggested a doping-dependent order parameter and the existence of a Quantum Critical Point (QCP) near optimum doping . In the electron doped (n-doped) HTSC, the prior PCS and tunneling data has been more controversial and there is no consensus at present on the implications of the data. The reason is the absence of a zero bias conductance peak (ZBCP) in the tunneling spectra  which argues against the presence of $`d`$-wave pairing symmetry while other types of experiments  support a $`d`$-wave pairing symmetry. In this paper, we present more detailed PCS experiments on the n-doped HTSC Pr2-xCexCuO4 (PCCO) in an attempt to better understand the pairing symmetry in the n-doped HTSC at all doping levels.

The theory of quasiparticle tunneling in a point contact junction between a normal metal and a conventional BCS-type superconductor has been developed by Blonder, Tinkham and Klapwijk (BTK) . In the BTK model, the superconductor is assumed to have an isotropic gap in momentum space. The barrier between the normal metal and superconductor is modelled by a delta function. The strength of the delta function is characterized by a dimensionless parameter $`Z`$. The $`Z=0`$ limit signifies a completely transparent junction while $`Z>>1`$ is the tunneling limit. This model has been very successful in explaining the features of the $`GV`$ spectra for tunneling in conventional $`s`$-wave superconductors . Fig. 1a shows calculated $`GV`$ characteristics for different barrier strengths.

The BTK model has been modified by Tanaka and Kashiwaya  for tunneling in superconductors with $`d`$-wave symmetry of the order parameter. The gap in a superconductor with $`d`$-wave symmetry is of the form $`\mathrm{\Delta }_\text{k}`$=$`\mathrm{\Delta }_0`$Cos(2$`\theta _\text{k}`$) where $`\theta _\text{k}`$ is the angle of a wave vector on the Fermi surface relative to . The order parameter is anisotropic and changes sign in momentum space. Constructive interference between the electron-like and hole-like quasiparticles, which experience different signs of the order parameter, results in formation of surface bound states at the Fermi energy . These surface bound states are also referred to in the literature as Andreev bound states (ABS) and lead to enhancement of tunneling conductance at zero bias. The ZBCP is expected for tunneling into the $`ab`$-plane for all surfaces except $`(100)`$ and $`(010)`$. The ZBCP reaches maximum height for tunneling into (110) family of planes and Fig. 1b shows the tunneling spectra for such case. The $`GV`$ tunneling spectra in $`d`$-wave superconductors are direction-dependent assuming a specular interface between the normal metal and superconductor. However, in practice the surface of the superconductor is rough on the atomic scale and this results in contribution to the tunneling current from facets of various orientations. When the effect of surface roughness is taken into account , the $`GV`$ spectra for tunneling into $`(100)`$ and $`(010)`$ planes also exhibit a ZBCP. ZBCPs have been observed in hole-doped HTSC, most notably and consistently in YBa2Cu3O7-δ (YBCO) for tunneling both into $`(100)`$ and $`(110)`$ orientations .

The order parameter symmetry may be more complicated than simply $`s`$-wave or $`d`$-wave, especially at the surface. This is of relevance because PCS essentially probes surface electronic states. The theory for tunneling into superconductors with more complex pairing symmetries, for example, anisotropic $`s`$-wave, extended $`s`$-wave and $`d+is`$ has also been developed .

While most of the cuprate superconductors have holes as their charge carriers, the family of cuprate superconductors $`R_{2x}`$CexCuO4 ($`R`$ = La, Nd, Pr, Sm, Eu) is unique in the sense that its carriers are predominantly electrons. Several early tunneling spectroscopy and PCS experiments were performed on optimally-doped Nd1.85Ce0.15CuO4 (NCCO)  to investigate the density of states and pairing symmetry of this compound. All these experiments revealed a gap-like feature in the $`GV`$ spectra of NCCO with no hint of a ZBCP due to ABS. This led to the conclusion that the pairing symmetry for NCCO was not $`d`$-wave but either conventional or anisotropic $`s`$-wave, in stark contrast to the hole-doped HTSCs. However, two recent PCS and Scanning Tunneling Spectroscopy (STS) experiments have observed ZBCP in optimally-doped NCCO . Recently, we presented PCS data on under-doped PCCO which provided convincing evidence for a ZBCP due to ABS . In that work, evidence for a doping-dependent pairing symmetry was also presented.

Meanwhile, penetration depth experiments on NCCO also supported the $`s`$-wave scenario . However, it was later realized that the magnetic moment of the Nd3+ ions would influence these measurements and might point to a misleading conclusion. Subsequent experiments on the related optimally-doped compound, PCCO , which is not plagued by the magnetic moment problem, provide evidence for $`d`$-wave symmetry. However, other penetration depth experiments on optimally-doped PCCO and NCCO  are more consistent with $`s`$-wave pairing symmetry. The work of Skinta et al.  also presents evidence for a doping dependence of the pairing symmetry.

Strong evidence of $`d`$-wave symmetry for optimally-doped NCCO and PCCO was provided by the phase sensitive tri-crystal grain boundary junction (GBJ) experiment , angle-resolved photoemission (ARPES) measurements  and Raman spectroscopy . However, these experiments, like tunneling and penetration depth measurements, are to some extent sensitive to the surface of the sample and there is the issue that the surface may be different from the bulk. Moreover, the doping near the grain boundaries may be different from that in the bulk and could influence the results of the tri-crystal GBJ and the GBJ tunneling experiments. Measurements of bulk properties were expected to finally resolve the question of the pairing symmetry but the results have yet to converge. A very small residual linear term in thermal conductivity measurements of PCCO crystals is evidence for absence of nodes in the gap and does not lend support to a pure $`d`$-wave pairing symmetry . Several explanations have been put forward for the absence of the residual linear term including the presence of a complex order parameter and localization of $`d`$-wave quasiparticles. The other bulk measurement, specific heat, argues in favor of dirty $`d`$-wave pairing symmetry . The term ‘dirty $`d`$-wave’ refers to a $`d`$-wave pairing symmetry in a superconductor which contains impurities leading to physical properties that deviate from those of a clean $`d`$-wave superconductor.

To summarize, despite strong evidence for a $`d`$-wave symmetry, there is no consensus on the nature of the pairing symmetry in optimally doped PCCO and NCCO. The most recent PCS and penetration depth data favors a doping-dependent pairing symmetry for these materials: $`d`$-wave for under-doped and $`s`$-wave for over-doped. In this paper we carry out an extensive investigation with PCS on PCCO thin films below their superconducting transition temperatures ($`T_c`$). We study the $`GV`$ characteristics as a function of cerium doping, magnetic field and barrier strength ($`Z`$).

## II Experimental method

PCCO thin films were used for PCS because better control and homogeneity of cerium is achieved in thin films compared to ceramic samples and single crystals. We have grown c-axis oriented PCCO thin films on Strontium Titanate (STO) and Lanthanum Aluminate (LAO) substrates using pulsed laser deposition. Details of film growth have been published elsewhere . Superconducting thin films of PCCO with cerium concentrations of $`0.13`$ (under-doped), $`0.15`$ (optimally-doped) and $`0.17`$ (over-doped) were grown. The films have a thickness of $`25003000\AA `$. The films were characterized by resistivity, AC susceptibility and X-ray diffraction measurements. The Tc for the under-doped, optimally-doped and over-doped films as determined from AC susceptibility and resistivity measurements are in the range $`12\pm 1K`$, $`21\pm 0.5K`$ and $`14\pm 1K`$ respectively.

The ‘spear on anvil’ technique is widely used for making the point contact junction. A sharp metal tip is carefully brought into contact with the superconductor and the barrier strength is controlled by varying the pressure of the contact with a screw mechanism or a transducer (see, for example, the reviews in Ref. ). In some cases, the sharp tip of a superconducting material has been employed with the normal metal as the counter electrode . However, this method is difficult to implement in our experiment for the following reasons. Only c-axis superconducting PCCO thin films can be grown. Attempts at growing a-axis and $`(110)`$ oriented superconducting PCCO films have not been successful. Since we want to tunnel into the $`ab`$-plane of this material and the thickness of the films is only $`3000\AA `$, a great deal of difficulty is encountered, not only in positioning the normal metal tip on the edge of the film, but also in varying the contact pressure without the tip slipping off the film edge. Hence, we have devised an alternative technique for PCS in the $`ab`$-plane of thin films and have designed and constructed a new probe for this purpose. We also note that a variation of this alternative method has been employed successfully in the past for PCS on superconductors .

A schematic side view of our point contact technique is depicted in Fig. 2. The film is cleaved in air to expose a fresh edge, electrical contacts on the film are made with Ag-In and it is glued with a quick-setting epoxy to a sapphire base. The film is placed in our PCS probe and a Au or Pt-Rh alloy wire of $`0.25mm`$ diameter, oriented perpendicular to the plane of the film, is carefully brought into contact with the cleaved edge of the film. The point contact junction is formed between the wire and the sharp edge of the film. The PCS probe is placed in a Helium-4 bath which can be pumped down to 1.4 $`K`$. In order to study the effect of the magnetic field on the point contact spectra and to drive the PCCO into the normal state, the film is placed with its ab-plane perpendicular to the magnetic field. In this orientation the Hc2 of our optimally-doped PCCO films is 8 $`T`$ (at 1.4 $`K`$) and this ensures that the film goes into the normal state at fields achievable in our laboratory. Therefore, a bevel gear arrangement is required to change the direction of motion for the point contact to be made. The Au or Pt-Rh wire is glued to a sapphire piece which in turn is glued to the threaded ‘nut’ on the shaft. The bevel gears can be rotated from outside of the Helium-4 bath. When the bevel gears rotate, the ‘nut’ along with the wire moves towards the edge of the film. The point contact can be made this way and the pressure of the contact can also be varied. A high pitch anti-backlash worm gear arrangement at the top part of the probe outside the Helium-4 bath ensures that the distance between the wire and the film edge can be controlled to sub-micron precision. One important advantage of this method over the ‘spear on anvil’ method is that the point contact is relatively stable against mechanical perturbations because the wire is also supported by the edge of the substrate. We make a four probe measurement to obtain the ($`IV`$) characteristics of our junctions and numerically differentiate it to obtain the conductance. We also use a standard lock-in technique to obtain the $`GV`$ spectra directly.

## III Results and discussion

Since our method of making point contact is unconventional, we decided to demonstrate its validity and effectiveness by doing PCS on optimally-doped c-axis oriented YBCO thin films in the same configuration that we have used for PCS on PCCO. The reasons for choosing YBCO for this purpose are that YBCO is an HTSC like PCCO and there is a consensus that the pairing symmetry of optimally-doped YBCO is predominantly $`d`$-wave and a ZBCP due to ABS has been observed in tunnel junctions and point contact junctions . The YBCO films have a thickness of 2000 $`\AA `$ and were grown on STO and Neodymium Gallium Oxide (NGO) substrates. The films have Tc in the range $`89.5\pm 0.5K`$. Since the $`GV`$ spectra for a superconductor with $`d`$-wave pairing symmetry are orientation-dependent, the films were cleaved in different directions. However, we find no major difference in the features of the $`GV`$ spectra for different cleavage orientations which suggests that surface roughness at the atomic scale leads to averaging of contributions from facets oriented in various directions.

Figure 3 shows the $`GV`$ characteristics for point contact tunneling into the ab-plane of YBCO with Pt-Rh alloy wire as the counter-electrode. One can see from the zero field data that the width of the ZBCP is 6 meV and the coherence peaks appear at the gap value of 18 meV. This is qualitatively similar to what is observed in PCS and Scanning Tunneling Spectroscopy (STS) on YBCO thin films and crystals  and confirms the validity and effectiveness of our point contact method.

We also studied the effect of c-axis oriented magnetic field on the ZBCP as shown in Fig. 3. We saw no splitting of the ZBCP at low fields unlike what has been reported for tunnel junctions . We observe that the peak splits explicitly in a magnetic field of 8 $`T`$. The origin of the ZBCP splitting in YBCO is still a matter of debate . However, direct splitting of the ZBCP in a magnetic field has not been observed in other tunneling experiments . Two of the possible reasons for the absence of splitting of the ZBCP at low fields are that the orientation of the films and surface morphologies of the junction interface are different from those in tunneling experiments in Ref. . In our experiment, the magnetic field is along the c-axis and perpendicular to the plane of film. Therefore, vortices enter the film even at very low magnetic fields due to the large demagnetization factor and hence the Meissner currents become almost field independent. The entry of vortices into the film at low fields probably marginalizes the role that Meissner currents are expected to play in the splitting of the ZBCP. Also, it is theorized that the splitting due to a sub-dominant order parameter ($`is`$ or $`id_{xy}`$) may be suppressed for rough junction interfaces, especially if the sub-dominant order parameter is $`id_{xy}`$ . A third reason for the absence of splitting at low fields in our experiment may be that the splitting of the ZBCP is expected to occur above a critical field whose magnitude is proportional to the transmissivity of the junction . Furthermore, the transmission coefficient decreases exponentially with increasing barrier strength . Since our point contact junction is more transparent than a tunnel junction, the fields for which we observe splitting are larger than those observed in experiments with tunnel junctions. We also note that the magnitude of the splitting is 2.1 $`meV`$ at 8 $`T`$ in our experiment which is in fairly good agreement with the magnitude of the indirect splitting in Ref. . The above discussion on the splitting of the ZBCP in a magnetic field has important implications for our data on PCCO.

We have performed a systematic and exhaustive study of PCS in the $`ab`$-plane of superconducting PCCO thin films of different cerium concentrations and have observed the $`GV`$ spectra for different barrier strengths and in magnetic fields. We have made point contacts on films with different nominal cleavage orientations. More than fifty point contact junctions have been studied.

For PCS in PCCO films with $`0.13`$ cerium concentration, we observe a ZBCP at low junction resistances and we have studied the ZBCP in a magnetic field applied normal to the ab-plane of the film. The data is shown in Fig 4. The shape and magnitude of the ZBCP suggest that it originates due to ABS and we have fitted the zero field data to a calculated $`d`$-wave $`GV`$ spectrum in Fig 4a. The fit takes into account the temperature dependence of the Fermi function. Besides the gap value ($`\mathrm{\Delta }`$) and the barrier strength (Z), the fitting parameters include the quasiparticle lifetime broadening parameter ($`\mathrm{\Gamma }`$), and the angle between the normal to the junction interface and the direction of the maximum gap ($`\alpha `$). The ZBCP is completely suppressed for magnetic fields in excess of $`H_{c2}`$ which is about 4 $`T`$, lending further support to the argument that the ZBCP is related to the superconductivity of the PCCO. Compared to the $`GV`$ spectra on YBCO, the ZBCP is not accompanied by a gap-like feature because of the low barrier strength of this normal metal/PCCO junction. The magnitude and width of the ZBCP decreases with increasing magnetic field  and the ZBCP does not split. The possible reasons for the absence of splitting of the ZBCP in PCCO are the same as those advanced earlier for YBCO. Moreover, the fact that we do not observe splitting of the ZBCP at all in PCCO may be due to a combination of two phenomena: low Z of our junction and the low $`H_{c2}`$ of PCCO compared to YBCO. Therefore, the absence of splitting of the ZBCP in a magnetic field in under-doped PCCO is not unexpected.

Fig. 5 shows some representative $`GV`$ spectra for PCCO $`x=0.13`$ for different junction resistances. For a high junction resistance which implies a higher barrier strength, we observe a gap-like feature with coherence peaks at the gap value. This can be seen more clearly in the inset (Fig. 5a). As the junction resistance is decreased, a ZBCP appears along with the gap-like feature shown in greater detail in the inset (Fig. 5b). For even lower junction resistance (and lower Z), a pronounced ZBCP is seen whose width is the same as the value of the gap as deduced from the fit in Fig. 4a. We have observed ZBCPs for low junction resistances in approximately 30 percent of our junctions and we believe the ZBCP appears when the normal metal electrode is able to penetrate the native surface barrier and make direct contact with the superconductor. For a junction with high barrier strength in a $`d`$-wave superconductor, theory predicts a sharp and pronounced ZBCP (see Fig. 1b) which we have never observed in our experiments on high Z junctions.

How do we explain this unusual $`Z`$-dependence of the $`GV`$ spectra? One possibility is the presence of an induced order parameter at the surface for junctions with low transmission coefficient (i.e. high Z). This suggestion is based on the paper by Tanuma et al.  who have proposed that for a high-Z junction in a $`d`$-wave superconductor, the $`d_{x^2y^2}`$ order parameter is suppressed at the surface and the spectral weight is transferred to a sub-dominant $`is`$ or $`id_{xy}`$ order parameter. This effect is maximum for tunneling into (110) orientation of the junction interface. We believe that in the case of PCCO, the magnitude of this induced order parameter exceeds the bulk $`d_{x^2y^2}`$ order parameter at the surface, which is plausible according to the theoretical calculations in Ref. . Therefore, we attribute the gap-like feature in the high-$`Z`$ limit to an induced order parameter whose magnitude ranges between 3 $`meV`$ and 5 $`meV`$ as estimated from the separation of the coherence peaks in several of the $`GV`$ spectra (for example, see Fig. 5a). We note that this induced order parameter is not present in the low-Z junctions and the ZBCP we observe is due to the $`d`$-wave nature of the bulk order parameter whose magnitude from the fit in Fig. 3a is 6 $`meV`$. Another possible explanation for the absence of the ZBCP in junctions with high-$`Z`$ is that disorder suppresses the ZBCP. This is based on the results of the experiment on tunnel junctions on YBCO in which the effect of disorder on the ZBCP was studied . However, in that experiment, the gap-like feature disappears along with the ZBCP as disorder increases. Since a pronounced gap-like feature is seen in our high-$`Z`$ data, we think it is unlikely that the absence of a ZBCP is solely due to disorder.

Although the simplest and most likely explanation of the ZBCPs in under-doped PCCO junctions is the $`d`$-wave pairing symmetry, we want to point out that ZBCPs due to ABS are predicted for other exotic symmetries (e.g. extended $`s`$-wave, $`d+s`$ with $`d>s`$) . The surface orientation dependence of the $`GV`$ spectra predicted for the above order parameters is different for each one but we are unable to distinguish between these by our experimental method because our $`GV`$ spectra are an average of contributions from facets of various orientations on the atomic scale. The existence of roughness at the atomic scale is supported by our observation that we find no qualitative change in the spectra for tunneling into different surface orientations.

The point contact spectra for optimally-doped and over-doped PCCO for different junction resistances are shown in Fig. 6 and Fig. 7 respectively. The $`GV`$ features are similar for these two doping levels and we will discuss these together. For high resistance junctions we see gap-like features with coherence peaks at the gap values. This is consistent with previous PCS and tunneling experiments on optimally-doped NCCO and PCCO  where no ZBCP was observed. For lower junction resistances and hence lower barrier strengths, we do not observe a ZBCP which suggests the absence of ABS at the Fermi energy. The shape of $`GV`$ spectra are now influenced by Andreev reflections and qualitatively resemble those of $`s`$-wave superconductors in the low/intermediate Z limit (see Fig. 1a). In general, a dip in the conductance at zero bias in low $`Z`$ junctions suggests absence of nodes in the order parameter . Therefore, keeping in view the shape of our $`GV`$ spectra for low $`Z`$ junctions on under-doped, optimally-doped and over-doped PCCO, we propose a transition from a $`d`$-wave order parameter for under-doped PCCO to a nodeless gap for optimal and over-doped PCCO. As an example, we have fitted the $`GV`$ data for the lowest junction resistance on over-doped PCCO to the generalized BTK model with isotropic gap as shown in Fig. 8a. A slightly better fit is obtained with a $`d+is`$ pairing symmetry calculation, with equal weights of the real and imaginary parts of the order parameter as shown in Fig. 8b. Both fits include the effect of thermal broadening. In calculating the best fit to the data, the lifetime broadening parameter ($`\mathrm{\Gamma }`$) is kept as small as possible and the angular integral is taken over the full range $`\pi /2<\theta <\pi /2`$. The purpose of the fits is to show that in both models the $`s`$-wave component has the same magnitude and that the low bias characteristics of the $`GV`$ spectra are determined to a large extent by the $`s`$-wave component of the order parameter. We also tried a fit to $`d+id_{xy}`$ pairing symmetry model with the same constraints on $`\mathrm{\Gamma }`$ and $`\theta `$ as in the $`d+is`$ model. However, given the physically reasonable constraints on $`\mathrm{\Gamma }`$ and $`\theta `$, the data could not be fit to the $`d+id_{xy}`$ model.

Our data points to a transition in pairing symmetry with doping and this suggests the existence of a Quantum Critical Point (QCP) at or near optimum doping. For $`d`$-wave superconductors, theoretical considerations limit the pairing symmetry transition across a QCP from $`d`$-wave to either $`d+is`$ or $`d+id_{xy}`$ . Our low $`Z`$ data on PCCO is more consistent with a $`d`$ to $`d+is`$ pairing symmetry transition across a QCP near optimum doping. A recent report also suggests a transition in pairing symmetry across a QCP near optimum doping in YBCO. .

It has been suggested that the proximity effect for transparent junctions on $`d_{x^2y^2}`$ superconductors leads to an induced $`s`$-wave order parameter in the normal electrode . This effect is maximum for $`(100)`$ or $`(010)`$ surface orientations and does not occur for $`(110)`$ orientation. If the absence of a ZBCP in our low $`Z`$ data on optimally-doped and over-doped PCCO is attributed to an $`s`$-wave order parameter being induced in the normal electrode due to the proximity effect, then it is difficult to understand why this effect is not observed in our low $`Z`$ junctions on under-doped PCCO. Therefore, we do not think our data can be explained by an $`s`$-wave order parameter induced by the proximity effect. Hence, the $`d+is`$ order parameter appears to be a property of the surface of optimally-doped and over-doped PCCO.

One interesting and puzzling aspect is the dependence of the gap-like features on the barrier strength and this can be seen in Fig. 6 as well as in Fig. 7. The energy scale of the gap-like features is equal to half the separation of the coherence peaks or maxima on either side of zero voltage bias. For over-doped PCCO, the energy of the gap-like feature in the tunneling limit is 3.2 meV while in the low $`Z`$ limit we obtain a value of 1.4 meV. For optimally-doped PCCO, the energy of the gap-like feature in the tunneling limit is 5 meV while in the low $`Z`$ limit it is 3.3 meV. We do not fully understand this phenomenon. However, we attempt to give a reasonable explanation. It is possible that the effect of nano-scale roughness at the place of the junction and the extent of the tunneling cone for quasiparticle injection change with the barrier strength. This may lead to gap-like features appearing at somewhat different energies in the spectra for junctions with different barrier strengths.

We have also studied the dependence of the $`GV`$ spectra in the tunneling limit on the magnetic field applied perpendicular to the plane of the film (i.e. parallel to the c-axis of the film) and present our data in Fig. 9a and 9b. Note that the coherence peaks are completely suppressed at 3 T for optimally-doped PCCO and 2 T for over-doped PCCO. These fields are less than $`H_{c2}`$ which is 8 T for optimally-doped PCCO and 4 T for over-doped PCCO. We have no explanation for this unusual field dependence at the present time. Notice that the magnitude of the superconducting gap decreases with increasing magnetic field and it evolves into a gap-like feature, qualitatively different from the superconducting gap, at $`HH_{c2}`$. We interpret this dip in the density of states at the Fermi energy as a normal state gap whose origin has not yet been determined conclusively and which has been discussed in detail in one of our earlier papers .

Finally, we would like to comment on whether our point contact junctions are in the ballistic (or Sharvin) limit i.e the contact radius ($`a`$) is much less than the mean free path ($`l`$) . This is considered an important criteria for the validity of PCS. The Sharvin formalism was originally developed to model transport across a micro-constriction between two similar metals . This formalism was extended by Wexler to the case where the micro-constriction has a ballistic as well as a thermal (Maxwell) part . Both the Sharvin and Wexler formulas have been employed in previous works for calculating the contact radii for point contact junctions between a metal and an HTSC. However, there is much debate on whether the Sharvin and Wexler formulas are applicable in their present forms to a point contact junction between two materials with very different Fermi liquid parameters and resistivities , as is the case with a normal metal and a high Tc superconductor. Moreover, since the high Tc superconductors have low mean free paths of the order of tens to hundreds of angstroms, the criterion for point contacts being in the Sharvin limit ($`a<<l`$), as estimated from the Sharvin and Wexler formalisms, have rarely been strictly achieved and in most cases the contact radius is either comparable to or greater than the mean free path in the superconductor . Authors have explained this by either considering the less rigorous condition ($`a<l`$) as sufficient for a ballistic contact, or suggesting that this leads to a higher effective $`Z`$, or postulating the existence of several parallel ballistic contacts. Whatever the case may be, there is some agreement that if the point contact is dominated by the thermal part, its conductance will decrease appreciably at higher voltage bias ($`eV>\mathrm{\Delta }`$) due to localized heating . In our $`GV`$ spectra, the conductance at higher voltage bias is either flat or increasing with voltage. Thus, we conclude that our point contact junctions are not in the Maxwell regime and the quasi-particle transport through the junctions is predominantly ballistic. This is a sufficient condition for energy-resolved spectroscopy of point contact junctions.

## IV Conclusion

For low barrier strength junctions on under-doped PCCO, we observe a ZBCP and show that it is due to $`d`$-wave pairing symmetry. We do not observe a ZBCP in low $`Z`$ PCS data on optimally-doped and over-doped PCCO and this indicates absence of nodes in the gap. Our data, along with theoretical considerations, indicates a $`d+is`$ pairing symmetry for optimally-doped and over-doped PCCO. We find that our data for low barrier strength junctions for all doping levels can be best explained by a $`d`$\- to $`d+is`$ pairing symmetry transition across optimum doping. This indicates the presence of a QCP near optimum doping for PCCO.

We observe gap-like features for high barrier strength junctions for all doping levels. For high Z junctions on under-doped PCCO, we believe that the $`d`$-wave order parameter is suppressed at the surface and the spectral weight is transferred to an $`is`$ order parameter which leads to gapped spectra. For high $`Z`$ junctions on optimally-doped and over-doped PCCO, the gap-like features are due to a fully gapped Fermi surface. The data on low $`Z`$ junctions on over-doped PCCO suggests that a $`d+is`$ order parameter leads to this nodeless and fully gapped Fermi surface. Indeed, data from all the previous PCS and tunneling experiments on NCCO and PCCO, which consistently showed a gap-like feature can be explained by an induced $`is`$ order parameter at the surface of under-doped PCCO, and by an order parameter without nodes for optimally-doped and over-doped PCCO.

We have studied the $`GV`$ spectra in magnetic fields up to and greater than $`H_{c2}`$ of PCCO. We find that the ZBCP in the $`GV`$ spectra of under-doped PCCO does not split in magnetic fields up to $`H_{c2}`$. This may be due to one or more of the following reasons: immediate penetration of vortices into our films; surface roughness of our junctions; the high transmissivity of our junctions. For $`H>H_{c2}`$, we observe a normal state gap at the Fermi energy in the $`GV`$ spectra in the tunneling limit for optimally-doped and over-doped PCCO. The normal state gap is of the same order of magnitude as the superconducting gap but differs qualitatively from it. The normal state gap is at least an order of magnitude less than the pseudo-gap that has been observed in other experiments on NCCO .

The authors acknowledge useful discussions with C. J. Lobb, S. M. Anlage and P. Fournier. We would like to thank the following colleagues: J. S. Higgins and M. C. Sullivan for assistance with PCCO and YBCO film growth, and Hamza Balci and Z. Y. Li for some of the PCCO ceramic pellets. This work was supported in part by NSF DMR 01-02350.