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# Asymptotic models of meridional flows in thin viscous accretion disksResearch supported by the Israel Science Foundation, the Helen & Robert Asher Research Fund and by the Technion Fund for the Promotion of Research

## 1 Introduction

The Shakura-Sunyaev (hereafter SS) model of geometrically thin steady accretion disks has extensively been used, since its publication (Shakura & Sunyaev ss (1973)), to model disks in a variety of astronomical objects. In particular, accretion disks, widely accepted to be present in mass transferring close binary systems (like CV - cataclysmic variables) and in young, still accreting, stars (like classical T-Tauri), were modeled using the SS paradigm and the calculated emerging spectrum was compared with observations. The SS model, which is based on the now famous $`\alpha `$ viscosity prescription, was found to be quite successful in reproducing at least the gross features of the observations and because of its relative simplicity and successful applicability it has achieved the status of a text-book paradigm (see e.g. Frank, King & Raine fkr (2002)).

Two key ingredients facilitate the SS approach - the $`\alpha `$ viscosity prescription and the assumption that the vertical extension of the disk is very small as compared to any significant radial scale. The second of these is viable if the cooling of the disk material (by radiative processes) is very efficient, so that the sound speed $`c_s`$ is very much smaller than the corresponding swirling flow velocity $`r\mathrm{\Omega }`$, which itself is close to the Keplerian velocity. Choosing a representative typical value for the radius $`\stackrel{~}{r}`$ and denoting the sound speed at that radius by $`\stackrel{~}{c}_s`$, we obtain a natural small parameter for the problem $`ϵ\stackrel{~}{c}_s/(\stackrel{~}{\mathrm{\Omega }}\stackrel{~}{r})`$, where $`\stackrel{~}{\mathrm{\Omega }}`$ is the Keplerian angular velocity at the representative point.

The SS model can naturally be understood in this context as the lowest order (in $`ϵ`$) approximation (see Regev 1983), but it requires also some consideration of the vertical structure, because the radiation (at least in the optically thick case) escapes essentially in the $`z`$ direction. The common practice to treat accretion disks using the SS paradigm has thus always been accompanied by vertical ”averaging” or ”integration”, that is, an effective elimination of the $`z`$ dependence from the equations. This gave a set of ordinary differential equations (ODE) in $`r`$ whose solutions provide the disk structure.

Studies wishing to model more accurately phenomena beyond the SS model, like time-dependent behavior, radiatively driven mass loss, various instabilities etc. have stretched the SS model to its limits, but the trend was to stay within the vertical averaging practice, because of the simplifications it introduces. For a fairly recent review of such applications see e.g. Lin & Papaloizou (linpap (1996)).

The question of the origin of the viscosity and the correct implementation thereof has also been the subject of extensive research efforts. The present day concensus identifies the magneto-rotational instability (Balbus & Hawley baha1 (1991)) as the source of MHD turbulence, which ultimately produces angular momentum transport (see Balbus & Hawley baha2 (1998) for a review). Although it seems that the classical $`\alpha `$ prescription is consistent with this process for vertically averaged thin accretion disks (Balbus & Papaloizou bapap (1999)), it is still unclear what the adequate model is to use in multi-dimensional time-dependent studies, as it was recently pointed out by Hawley, Balbus & Stone (hbs (2001)). This work actually addresses nonradiative accretion flows (NRAF), that is, flows in which the radiative cooling time is very long compared to the time scales of interest. Previous studies in this context introduced the so-called ADAF (Narayan & Yi 1994, Abramowicz et al. 1995) and CDAF (see Abramowicz & Igumenshchev 2001 and references therein) giving rise to some controversy among the different researchers.

Our work here deals with a thin, efficiently radiating, disk and therefore seems to have no direct relation with the NRAF and associated problems. Still the robustness of our results (which hold in the polytropic and therefore adiabatic case as well) hints that backflows may have some consequences also in NRAF.

In the study of thin disks it is natural to employ systematic asymptotic expansions in the small parameter $`ϵ`$. Regev (bl (1983)), hereafter R83, introduced it for the purpose of calculating the structure of an accretion disk-star boundary layers and carried it out only in the lowest order. In that work, matched asymptotic expansions were used, and it developed into a full semi-analytic study of boundary layers in disks around T-Tauri stars. However, not only were these expansions done only up to the first order, but also the vertical structure of the disk (and the boundary layer) was averaged out (using the usual vertical integration procedures mentioned above).

Urpin (urpin (1984)) was intetested in finding an approximation for a steady accretion disk flow, beyond the SS solution, which provides only the average inflow velocity. He was able to get the two-dimensional approximate structure of the flow in the $`rz`$ plane. In doing this he demonstrated that consideration of the vertical gradients of the viscous stress tensor leads to a class of solutions in which the flow direction in the midplane of the disk may be opposite to that in the the layers around it, up to the disk surface. In Urpin’s work the viscous terms were not treated consistently (neglected in one of the equations, but retained in the other) and in addition a net zero angular momentum transport was assumed. Therefore he obtained backflows for all values of the viscosity parameter $`\alpha `$ and, in any case, his solutions are actually valid only for large radii.

Already the first attempts at a full two-dimensional hydrodynamical numerical simulations of radiative viscous accretion disks demonstrated that indeed the meridional flow cannot often be well described by the vertically averaged value of the velocity. In such calculations the result obviously depends on the outer boundary conditions. Kley & Lin (kleylin (1992)) found backflows near the midplane, similar to Urpin’s solutions, but have shown that if an inflow condition at the outer boundary is assumed, a circulation pattern is obtained. More detailed studies by Różyczka et al. (rozyczka (1994)) also exhibited flows with regions of midplane backflows and with circulation patterns.

Kluźniak & Kita (kk (1997)), hereafter KK, in a beautiful work, carried out expansions in $`ϵ`$ up to second order and considered the full viscous flow dynamics, but neglected thermal effects (which Urpin retained). Using a polytropic relation and an inner zero torque boundary condition, they obtained global analytical solutions with backflows. In these solutions the location of the flow stagnation point on the equator $`r_{\mathrm{stag}}`$ was found as a function of the viscosity parameter $`\alpha `$.

In the present paper we would like to present the results of asymptotic semi-analytical calculations of steady thin accretion disks, similar to the ones obtained by KK, but with thermal effects explicitly included via an energy equation, containing viscous dissipation and radiative losses (treated in the diffusion approximation). The inclusion of the energy equation will force us to use some (quite straightforward) numerical ODE integrations and thus the solutions will not have the closed analytical form of KK.

## 2 Assumptions and equations

We use the standard assumptions of steady state, axial and equatorial symmetry, simplifying significantly the equations of viscous fluid dynamics when they are expressed in cylindrical coordinates.

Writing the equations in a non-dimensional form, that is, scaling all the variables by their typical values (denoted by tilde), brings out the non-dimensional constant $`ϵ`$. This constant was defined above and it reflects the disk thickness. It is thus a natural expansion parameter for a perturbative treatment of geometrically thin ($`ϵ1`$) disks.

Denoting the radial, vertical and azimuthal velocity (in cylindrical coordinates $`r,z,\varphi `$) by $`u`$,$`v`$ and $`r\mathrm{\Omega }`$ respectively, the statements of conservation of mass, angular momentum, horizontal and vertical linear momentum and energy, in steady state and with the assumption of axial symmetry, read:

$$ϵ\frac{1}{r}_r(r\rho u)+_z(\rho v)=0,$$
(1)
where $`\rho `$ is the mass density;

$$\frac{ϵu}{r^2}_r(r^2\mathrm{\Omega })+v_z\mathrm{\Omega }=\frac{ϵ^2}{\rho r^3}_r(\eta r^3_r\mathrm{\Omega })+\frac{1}{\rho }_z(\eta _z\mathrm{\Omega }),$$
(2)
where $`\eta \rho \nu `$ is the viscosity coefficient. We note in passim that this is, of course, the anomalous viscosity and it is assumed that irrespective of its source it can be parametrized using the usual (SS) $`\alpha `$ prescription, which allows us to express the viscosity coefficient using the well known Ansatz for the $`r\varphi `$ component of the viscous stress tensor

$$|\tau _{r,\varphi }|=\alpha p,$$
(3)
where $`p`$ is the pressure;

$$ϵ^2u_ru+ϵv_zu\mathrm{\Omega }^2r=f_{\mathrm{grav}}^rϵ^2\frac{1}{\rho }_rp+ϵf_{\mathrm{vis}}^r,$$
(4)
$$ϵu_rv+v_zv=f_{\mathrm{grav}}^z\frac{1}{\rho }_zp+f_{\mathrm{vis}}^z;$$
(5)
and

$$\frac{1}{\gamma 1}(ϵu_rT+v_zT)+T\left[ϵ\frac{1}{r}_r(ru)+_zv\right]=q_{\mathrm{vis}}^+q^{},$$
(6)
where $`T`$ is the temperature and $`\gamma `$ the adiabatic constant and where we have assumed that the disk material obeys the perfect gas equation of state.

Some additional symbols appear in the above equations and they are:

1. The gravitational force (per unit mass) components, given by:

$$f_{\mathrm{grav}}^r=\frac{1}{r^2}\left(1+\frac{ϵ^2z^2}{r^2}\right)^{\frac{3}{2}};f_{\mathrm{grav}}^z=\frac{z}{r}f_{\mathrm{grav}}^r.$$
2. The viscous force (per unit mass) components $`f_{\mathrm{vis}}^r;f_{\mathrm{vis}}^z`$ and the viscous energy dissipation rate (per unit mass) $`q_{\mathrm{vis}}^+`$. Since the expressions defining them are somewhat lengthy we shall refrain from giving them explicitly here and refer the reader to e.g. Tassoul (1978).
3. The energy loss rate (per unit mass) $`q^{}`$, whose form depends on the physical conditions. Assuming only radiative losses we get

$$q^{}=\mathrm{\Lambda }\frac{1}{\rho }\left[\frac{1}{r}_r(rF^r)+_zF^z\right],$$
(7)
where $`\mathrm{\Lambda }`$ is a non-dimensional constant and $`F^r`$, $`F^z`$ are the appropriate radiative flux components. If the disk is optically thick (as we shall assume in this work),the diffusion approximation for radiative transfer is viable and the radiative fluxes can be expressed in terms of the structure functions, temperature gradient and the opacity in the usual way (see R83).

## 3 Lowest order solutions - the SS disk

Expanding all the dependent variables in power series in $`ϵ`$ and denoting the succesive terms by the subscripts $`0,1,2\mathrm{}`$ it is quite easy to see (R83, KK) that in the lowest order we get

$$\frac{1}{r}_r(r\rho _0u_1)+_z(\rho _0v_2)=0,$$
(8)
because $`u_0=v_0=v_1=0`$,

$$r\rho _0u_1_r(r^2\mathrm{\Omega }_0)=_r(\eta r^3_r\mathrm{\Omega }_0),$$
(9)
$$\mathrm{\Omega }_0=r^{3/2},$$
(10)
$$_zp_0=\rho _0zr^3,$$
(11)
$$_zF_0=\mathrm{\Lambda }^1\eta r^2(_r\mathrm{\Omega }_0)^2,$$
(12)
where $`F_0F_0^z`$.

The SS solution can be easily recovered from these equations (see R83), but our aim here will be to obtain from them also the vertical structure, needed for the next order approximation. Like in the SS approach we vertically integrate equations (8) and (9) and get

$$_{\mathrm{}}^{\mathrm{}}r\rho _0u_1𝑑z=const\dot{m},$$
(13)
where the constant $`\dot{m}`$ is the nondimensional mass transfer rate, and

$$\dot{m}_r(r^2\mathrm{\Omega }_0)=_r(\mu r^3_r\mathrm{\Omega }_0),$$
(14)
where $`\mu _{\mathrm{}}^{\mathrm{}}\eta 𝑑z`$. Using now (10) we can integrate equation (14) on $`r`$ and use the condition that at some $`r=r_+`$ the zero torque condition is satisfied, that is, $`\mathrm{\Omega }`$ is at its extremum there (see KK). The result is

$$\mu =\frac{2}{3}\dot{m}\left(1\sqrt{\frac{r_+}{r}}\right).$$
(15)
The fact that a Keplerian angular momentum profile does not have an extremum and that it has to be joined somehow to a sub-Keplerian star gives rise to the boundary layer problem, which we shall avoid here by looking only at radii sufficiently larger than $`r_+`$.

To get the equations determining the vertical structure at each $`r`$ we use equations (11) and (12) and substitute in the latter the Keplerian $`\mathrm{\Omega }_0`$ (from equation 10). This gives

$$_zp=\rho zr^3,$$
(16)
$$_zF=\frac{9}{4\mathrm{\Lambda }}\eta r^3,$$
(17)
where we have dropped the subscripts $`0`$ from the functions, for convenience. Treating the radiation in the diffusion approximation we get the additional equation

$$_zT=\kappa \rho T^3F,$$
(18)
where $`\kappa `$ is the (properly non-dimensionalized) opacity, assumed known as a function of $`\rho `$ and $`T`$.

This set of three equations, supplemented by the equation of state $`p=\rho T`$, is sufficient in principle for the determination of the vertical structure at each radial point $`r`$, but appropriate boundary conditions are obviously also needed. This complicates matters, because whereas the lower boundary can be simply set at $`z=0`$, the upper one cannot be determined a priori. We chose to employ the Eddington approximation for this boundary condition. This approximation requires radiative equilibrium, that is no energy sources in the outer layers, and to achieve it we tacitly assume that the viscosity coefficient approaches zero for a small enough optical depth. Actually, our form of the viscosity parameter $`\eta `$ is obtained from the relation (3), which for the Keplerian (lowest order) $`\mathrm{\Omega }(r)`$ gives

$$\eta =\frac{2}{3}\alpha r^{3/2}p.$$
(19)
Typically, $`p`$ decreases with $`z`$ and therefore so does $`\eta `$. Thus using the Eddington approximation should be reasonable, at least in the optically thick case, as long as we ignore possible instabilities which may result in winds and coronae (see Shaviv, Wickramasinghe & Wehrse 1999).

Explicitly, if we define the outer (vertical) limit of the disk and hence of our integration as $`z_{\mathrm{out}}`$ (see below), the integration of equation (17) from $`z=z_{\mathrm{out}}`$ to $`z=z_{\mathrm{out}}`$ gives

$$F(z_{\mathrm{out}})=\frac{9}{8\mathrm{\Lambda }}\mu r^3=\frac{3}{4\mathrm{\Lambda }}\dot{m}r^{7/2}(r^{1/2}r_+^{1/2}),$$
(20)
where the second equality follows from (15). This is the upper boundary condition on the flux, but the value of $`z_{\mathrm{out}}`$ has still to be specified. The lower boundary condition on the flux is much simpler as it is just $`F(z=0)=0`$.

The Eddington approximation links the radiative flux and the temperature at the base of the photosphere ($`\tau _{\mathrm{dim}}=2/3`$) and this point is defined to be at $`z=z_{\mathrm{out}}`$, since the flux above it is constant. In its non-dimensional form, using our units, the Eddington condition reads

$$T^4(z_{\mathrm{out}})=\frac{8}{3\stackrel{~}{\tau }}F(z_{\mathrm{out}}),$$
(21)
where $`\stackrel{~}{\tau }=\stackrel{~}{\kappa }\stackrel{~}{\rho }\stackrel{~}{h}`$ is our optical depth unit.

The three equations (16-18) are thus solved as a two-point boundary problem subject to the four conditions $`F=0`$ at $`z=0`$; (20), (21) and $`p=0`$ at $`z=z_{\mathrm{out}}`$, where the value of $`z_{\mathrm{out}}`$ itself is also determined in an iterative way.

In figure 1 we show the result for $`\rho (r,z)`$ in a typical case ($`\alpha =0.2`$ and electron scattering, i.e. constant, opacity case). In this, and all subsequent figures the radial coordinate is scaled by $`\stackrel{~}{r}r_+`$ and the vertical one by $`\stackrel{~}{h}ϵr_+`$.

Figure 2 is the vertical temperature profile $`T(z)`$ for a representative radius value and two values of $`\alpha `$: $`0.4`$ (the solid line) and $`0.7`$ (the dotted line). As we shall see in the next section, these two cases differ radically in their meridional flow pattern, but we should stress that the temperature profiles described here are calculated in the lowest order and are, of course, not influenced by the flow.

The procedure outlined in this section provides the lowest order values of the disk structure functions $`p_0(r,z)`$, $`\rho _0(r,z)`$ and so on, which will be needed to solve for the flow pattern in the next order.

## 4 Higher order solutions - the meridional flow pattern

As explained above, the lowest order contributions to the meridional velocity componenets are of order $`ϵ`$ (i.e. $`u_1`$) and $`ϵ^2`$ (i.e. $`v_2`$) and it turns out that the lowest order correction to the Keplerian angular velocity is of order $`ϵ^2`$ ($`\mathrm{\Omega }_2`$) - see KK and Urpin (urpin (1984)). The relevant equations, following from the expansions and originating from the mass, angular momentum and horizontal momentum conservation equations are

$$_r(r\rho _0u_1)+r_z(\rho _0v_2)=0,$$
(22)
$$r\rho _0u_1_r(r^2\mathrm{\Omega }_0)=_r(\eta r^3_r\mathrm{\Omega }_0)+r^3_z(\eta _z\mathrm{\Omega }_2),$$
(23)
$$2r\rho _0\mathrm{\Omega }_0\mathrm{\Omega }_2=\frac{3z^2}{2r^4}\rho _0_rp_0+_z(\eta _zu_1).$$
(24)
Despite their appearance these equations can be viewed as ODE in $`z`$ for any given $`r`$, since $`p_0`$, $`\rho _0`$ and $`\mathrm{\Omega }_0`$, as well as $`\eta `$ are already known functions, from the lowest order solution for the vertical structure (as explained in the previous section). In addition, equation (22) can be decoupled from the other two, because one of the variables, $`v_2`$, appears only in it. Since equations (23-24) are of second order each, four boundary conditions are required. Two of them are obvious and are the result of equatorial symmetry:

$$_zu_1=0\mathrm{and}_z\mathrm{\Omega }_2=0;\mathrm{at}z=0,$$
(25)
for any $`r`$. The other two conditions result from a regularity requirement, that is, that $`u_1`$ and $`\mathrm{\Omega }_2`$ remain bounded for $`z\mathrm{}`$. In KK the density achieved a true zero for a finite value of $`z`$, owing this property to the polytropic assumption. In our case $`\rho _0`$ decays with $`z`$ and we have found that physically meaningful results are to be expected only if we require that both $`\rho _0u_1`$ and $`\rho _0\mathrm{\Omega }_2`$ are sufficiently small at $`z_{\mathrm{out}}`$. This expectation has been strengthened by testing our algorithm on the polytropic case and getting very good agreement with the analytical results of KK.

After the two equations (23-24) are solved, $`v_2`$ follows from the solution of the first order equation (22) with the initial condition $`v_2=0`$ at $`z=0`$.

The result of a representative calculation ($`\alpha =0.4`$ and electron scattering opacity) is shown in Figure 3. For this case we obtain a meridional flow pattern with a backflow around the equatorial plane. The stagnation radius is in this case $`r_{\mathrm{stag}}7.5r_+`$.

For other values of $`\alpha `$ the trend is similar to the one found by KK, that is, $`r_{\mathrm{stag}}`$ growing with $`\alpha `$ and for $`\alpha >\alpha _{\mathrm{crit}}`$ there are no solutions with backflows ($`r_{\mathrm{stag}}=\mathrm{}`$). While the disk structure depends somewhat on the opacity law (we have experimented with electron scattering opacity and Kramers opacity law), the meridional flow pattern and the stagnation radius (see below) are quite insensitive to it. In fact the relevant graphs (see below) for the abovementioned two opacity laws look indistinguishable and consequently we shall display only the electron scattering opacity case.

A case in which the stagnation radius is so large that it is not found up to $`r1000r_+`$ is shown in fig. 4, where $`\alpha =0.7`$. Note that even for these large values of $`r`$ the flow is directed inward everywhere.

The determination of the value of $`\alpha _{\mathrm{crit}}`$ can be achieved by calculating $`r_{\mathrm{stag}}`$ for a sequence of $`\alpha `$ values and finding where $`r_{\mathrm{stag}}(\alpha )`$ grows beyond any reasonable bound. Reasonable, in this context, means a radius beyond which the disk does not exist in a realistic astrophysical setting. In any case, when $`r`$ is very large the present numerical calculation cannot give reliable results because of the truncation error.

In Fig. 5 we show the stagnation radius for a number of $`\alpha `$ values and clearly see the trend that it grows beyond any reasonable bound for $`\alpha 0.7`$. It is interesting to note that our results are completely consistent with the analytical result of KK (solid line) found for polytropes. The meridional flow behavior seems to result thus from the dynamics rather than from thermal processes in the disk.

## 5 Summary

In this work we have included thermal effects in the scheme, previously proposed by Kluźniak and Kita (1997), to calculate the vertical structure of thin accretion disks (including the flow pattern) by perturbative analysis. The small parameter of the expansions is $`ϵ`$, reflecting the disk thickness. To the lowest order in $`ϵ`$ the SS solution is recovered and we obtain also the vertical pressure and temperature structure. The accretion flow is found from the next order and includes, for small enough values of the viscosity parameter, equatorial backflows.

These findings support the claim made by KK that the backflows are of dynamical, rather than thermal, origin and probably result from vertical gradients of the viscous stress tensor. Our result for the flow is obtained numerically, using two explicit initial condition at the disk mid-plane and two regularity conditions. The latter complete the constraints needed for the solution of a fourth order differential system. However, because these constraints are independent of $`r`$, our solutions are obtained for all $`r`$ values and cannot account for given detailed boundary conditions on the flow at some $`r=r_{out}`$.

Still, it is conceivable that if such conditions are imposed in a full numerical hydro simulation, our solution will be correct only for an intermediate region, situated between $`r_+`$ and $`r_{\mathrm{out}}`$, and not too close to these boundaries. Our solutions should smoothly join the outer flow pattern, which has to be consistent with the outer boundary conditions. For an outer boundary condition of inflow along all $`z`$, this should give rise to circulation patterns of the type observed in the numerical simulations of radiative disks cited in the introduction.

Although our results are formally valid only for very small $`ϵ`$ and for radiative (as well as polytropic, see KK) disks, it is reasonable (as is often the case in asymptotic analyses of this type) that they carry over also to cases of $`ϵ`$ close to unity. This means that quasi spherical flows, like the non-radiative ones (NRAF), may be endowed with circulation patterns as well. Whether these results are directly relevant to CDAF (if these flows are indeed proven to be viable) remains unclear. It can, however, be definitely stated that ADAF solutions using vertical averaging may not faithfully represent radial energy transport when there are substantial backflows, which naturally carry energy outwards in the hottest parts of the disk. In addition, we think that an approach of the kind reported here may provide useful tools for the understanding of some complicated features of flow patterns and instabilities in accretion disks.

## Acknowledgement

We would like to thank Wlodek Kluźniak for his remarks and suggestions which helped to improve this paper.


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# Identification of polymorphs of pentacene

## Introduction

Pentacene has recently gained interest as a molecular conductor with a very high electronic mobility. Mobilities of 1 cm2/Vs were reported at 300K, increasing to 104 cm2/Vs at low temperatures . Moreover, evidence for superconductivity up to 2 K in field effect devices was reported . We study the origin of this high mobility and its relation with the crystal structure, i.e. the stacking of the molecules. The crystal structure and growth of pentacene has been subject of a number of studies . Pentacene crystallizes in a layered structure with a herringbone arrangement within the layers, see Fig. 1. The layer periodicity, $`d`$(001),

is by far the largest repeat unit, and thus characteristic of the structure. In the early sixties, Campbell et al. determined the single crystal structure using a film method . These results were slightly modified , but yielded both a characteristic $`d`$(001) value of 14.4 Å. In 1991 Minakata et al. reported on the growth and crystal structure of thin films . They reported for thin films $`d`$(001)-spacings of 15.0 and 15.4 Å. It was only noticed by Dimitrakopoulos et al.  that these thin film polymorphs must be different from the single crystal. They also observed for the first time the coexistence of two phases, of 14.4 and 15.4 Å. The growth of these polymorphs was studied by Schoonveld et al. . These phases are generally referred to as the ”single crystal” and ”thin film” phase. We argue the former name to be incorrect as more recent redeterminations of the single crystal structure by Holmes et al. , Siegrist et al.  and by us  show the single crystal $`d`$(001) value to be 14.1 Å. Apparently there exist several polymorphs of pentacene. Identification of these pentacene polymorphs is especially important when the electronic properties are related to the crystal structure. Recent band structure calculations show that the electronic properties depend strongly on the particular stacking of the molecules within the layers . In this paper we discuss how the various polymorphs can be made, and what their crystal structures are. We identify four different polymorphs and determine by X-ray and electron diffraction their unit cell parameters. Of one of the polymorphs we determine the hole mobility, via space-charge-limited-current measurements on a single crystal.

## Experimental procedures

Thin films of pentacene were prepared by evaporation in a high vacuum environment of 10-7 mbar. The source material, pure pentacene was obtained from Aldrich and not further purified. It was placed in a tantalum crucible and heated to 540 K. As substrate thermally oxidized silicon ($`a`$-SiO2) or kapton (polyimide) was used. The substrate temperature was measured with an Al-Cr thermocouple and the substrate could be heated or cooled. The evaporation rate of the sublimed material was monitored by a quartz oscillator and the layer thickness was determined using a dektak. The evaporation was kept constant at a low rate of 0.1 nm/sec to ensure crystallinity. A shutter allowed the evaporation rate to become stable before the substrate was exposed to the pentacene flow.

Single crystals of pentacene were grown using a vapour transport method . A pyrex tube was thoroughly cleaned by heating it under a stream of pure nitrogen gas. 200 - 400 mg of unprocessed pentacene, obtained from Aldrich, was placed at one end of the tube in a platinum crucible. The growth was performed either under a stream of nitrogen gas mixed with hydrogen gas, with a volume percentage of 5.1(1)% hydrogen, or under an argon flow. Transport gases were obtained from AGA with 5N purity for N2 and Ar and 4N5 purity for H2. Great care was taken to avoid contamination with O2 and H2O. Nitrogen and argon gases were further purified over activated copper and alumina columns. A temperature gradient was applied by resistively heating two heater coils wrapped around the tube. Crystallization took place some 300 mm from the sublimation point at a temperature of approximately 490 K. Single crystals were also grown from a solution of trichlorobenzene (TCB). Violet crystals were obtained by slowly (four weeks) evaporating the TCB at 450 K, under a stream of ultra pure nitrogen gas.

The X-ray diffraction patterns of the obtained single crystals were measured with an Enraf-Nonius CAD-4 or a Bruker SMART APEX diffractometer. Both diffractometers use monochromated Mo - K$`\alpha `$ radiation. The structures are solved using SHELXS and SHELXL . The X-ray diffraction patterns of pentacene thin films were measured using a D8 powder diffractometer of Bruker A.G. in a Bragg-Brentano geometry, with monochromatic Cu-K$`\alpha _1`$ radiation. A variable temperature stage is used for in situ temperature dependent measurements between 100 K and 650 K, in a vacuum of 10-2 mbar. The obtained spectra were analyzed using the TOPAS software package . Electron diffraction (ED) measurements were performed on a Philips CM200/FEG (200 kV) transmission electron microscope. During the measurements the electron dose was held low, to prevent radiation damage of the samples. Experiments were performed in the Electron Microscopy group of the department of biophysical chemistry in Groningen and in the National Centre for HREM in Delft.

## Growth of the different polymorphs on thin films

In the literature different $`d`$(00l) values are reported for pentacene thin films . To investigate this, we have grown thin films of pentacene, using different growth conditions. A typical X-ray diffraction pattern of a pentacene thin film is shown in Fig. 2. The peaks can be indexed as $`\mathit{00}l`$ reflections, indicating a strong preferential alignment with the $`[\mathit{00}l]`$ vector perpendicular to the substrate.

In the inset of Fig. 2, parts of two diffraction patterns of two thin films, grown in different ways, are shown. We observe reflections centered at 5.80, 5.92, 6.19 and 6.33 degrees 2$`\theta `$. Analysis of the entire spectra shows the reflections to correspond to $`d`$(001) spacings of 14.1, 14.4, 15.0 and 15.4 Å. This result indicates that at least four polymorphs of pentacene are present in the various thin films.

Typically, two polymorphs are observed on one thin film sample, as shown in the inset of Fig. 2. However, single phased thin films can be grown. In literature the growth of the 14.4 and 15.4 Å polymorphs was reported to depend on the film thickness and the substrate temperature . We observe that the growth of the polymorphs depends also on the nature of the substrate. The 14.4 and 15.4 Å polymorphs grow on $`a`$-SiO2 substrates, whereas the 14.1 and 15.0 Å polymorphs grow on kapton. The top of the inset in Fig. 2 shows a part of a spectrum of a film grown on $`a`$-SiO2. In this spectrum we observe the 14.4 and 15.4 Å polymorphs. At the bottom of this figure, the pattern of a film grown on kapton is shown. Here, peaks correspond to the 14.1 and 15.0 Å polymorphs.

The 15.4 Å phase can be grown single phased if the film thickness remains below a certain critical value, which depends on the substrate temperature. This polymorph is typically grown at room temperature. The 14.4 Å phase is observed above this critical thickness, and at an elevated substrate temperature. The fraction of this polymorph increases with the film thickness . We observe that this dependence on the substrate temperature and the film thickness also holds for the 15.0 and 14.1 Å polymorphs. Here, the 15.0 Å polymorph is stable for small film thicknesses and low substrate temperatures.

Typical growth conditions to obtain single-phased films are listed in Table 1. We have grown single phased films of the 15.0 and 15.4 Å phases at ambient temperature with a film thickness of approximately 50 nm, on a kapton and $`a`$-SiO2 substrate, respectively. The 14.1 and 14.4 Å phases were observed single-phased on films grown at 370 K, with a thickness of $``$150 nm, on substrates of kapton and $`a`$-SiO2, respectively.

The spectrum on the top of the inset in Fig. 2 was of a 2 $`\mu `$m thick film. In this spectrum we observe not only two, but three polymorphs of pentacene. Besides the 15.4 and 14.4 Å polymorphs, the shoulder of the peak at 6.19 2$`\theta `$ could be recognized as belonging to the 14.1 Å structure. This suggests that the growth of the different phases on an $`a`$-SiO2 substrate is as follows. In the first $``$30 monolayers the 15.4 Å polymorph is formed, if the film becomes thicker also the 14.4 Å structure appears. If the film becomes extremely thick ($`>`$1300 monolayers), also the 14.1 Å phase is observed. The 14.1 Å structure is observed in single crystals and on thin films grown on polyimide. This substrate does, therefore, not seem to influence the growth. However, the appearance of the 14.1 Å polymorph on thick films on a $`a`$-SiO2 substrate indicates that the 14.4 and 15.4 Å polymorphs are substrate induced.

## Temperature dependence

We studied the possibility of structural phase transitions between 143 and 423 K. Firstly, a film of the 15.4 Å structure was measured at ambient temperature, slowly heated to 403 K and cooled down again. An irreversible change of the 15.4 Å phase into the 14.4 Å phase was observed. This structural change as function of temperature is shown in Fig. 3. In this figure relative intensities are shown, because above 370 K sublimation of the material started. This decreases the measured intensity and makes the structural change difficult to observe.

Heating a film containing both the 15.0 and the 14.1 Å phases, to 423 K, showed behaviour analogous to the 15.4 Å phase. At elevated temperatures the 15.0 Å phase changed irreversibly into the 14.1 Å structure.

We cooled and heated the 14.1 Å polymorph in single and poly-crystalline form. A full single crystal data set was measured at 90 K. However, no phase transition was observed. From the temperature dependence of X-ray spectra of powder of the 14.1 Å polymorph, in the range of 143 K to 475 K, we derive anisotropic linear coefficients of thermal expansion: $`\alpha _a`$ = -19 $``$ 10-6 K-1, $`\alpha _b`$ = 64 $``$ 10-6 K-1, and $`\alpha _c`$ = 53 $``$ 10-6 K-1.

A film containing only the 14.4 Å polymorph was slowly heated to 475 K, but no structural transition was observed. We cooled a sample containing both the 15.4 and the 14.4 Å polymorphs to 143 K. No structural changes were observed during the cooling process. Also a film containing the 15.0 Å and 14.1 Å polymorphs did not show any structural transition during cooling. From these experiments it can be concluded that the 14.1 and the 14.4 Å phases are thermally the most stable ones. The 15.0 and 15.4 Å structures can, at elevated temperatures, be transformed into the 14.1 and 14.4 Å phases, respectively.

It was already observed by Gundlach et al. that the 15.4 Å phase can be transformed into the 14.4 Å polymorph . They exposed their films of the 15.4 Å phase to solvents like acetone, isopropanol, and ethanol (in which pentacene does not dissolve) and noticed that the 15.4 Å phase almost completely changed to the 14.4 Å phase. We performed the same experiments and observed that indeed the 15.4 Å phase disappeared from the spectra. Since we lost some material in the process, it was not clear whether it was transformed into the 14.4 Å phase or had become amorphous. The same observation was made for the 15.0 Å polymorph, which transformed after exposing the film for $``$3 minutes to ethanol.

## The 14.1 Å polymorph: single crystals

Besides the growth of thin films, also single crystals were grown. Single crystals, grown in various ways, yield exclusively the 14.1 Å polymorph. Crystal growth from vapour transport yields almost centimeter sized violet crystals, in different forms: platelets and needles. These pentacene single crystals were measured on the CAD-4 diffractometer. Needle shaped crystals were observed to grow along the \[1$`\overline{1}`$0\] axis, whereas the platelets grow in the $`ab`$ plane. Both had a $`d`$(001) value of 14.1 Å. Pentacene single crystals grown from a solution of trichlorobenzene were analyzed on the APEX diffractometer. This yielded the same crystal structure as for the crystals grown using the vapour transport technique. The unit cell parameters are given in Table 2 and more details are reported elsewhere .

The vapour transport experiments did not result in single crystals of pentacene exclusively. The employed transport gases, and their flow rate, were of significant influence on the crystals. At a slightly lower temperature (480 K) than where the violet pentacene crystals crystallized, also red needles were grown. If excess hydrogen gas was used, more red crystals were observed. The crystallization point was $``$ 50 mm apart from the centre of the pentacene growth, which allowed physical separation of the two types of crystals. Single crystal diffractometry showed it to be a hydrogenated form of pentacene: 6,13-dihydropentacene, with two methylene groups at opposite sides of the middle ring. The structure can be described as a monoclinic unit cell containing four non-planar hydrogenated pentacene molecules and two planar pentacene molecules. The detailed crystal structure is described elsewhere .

At lower hydrogen content, or if no ultra pure inert transport gas was used, yellow-brown coloured crystals could be observed. They condense at a slightly higher temperature than the pure pentacene crystals, at $``$ 520 K. Analysis on the APEX diffractometer proved it to be an oxidized form of pentacene, 6,13-pentacenequinone, with two carbonyl groups at opposite sides of the middle ring. The unit cell is monoclinic, and described elsewhere , in agreement with literature .

## The 14.4 Å polymorph: powder diffraction

The 14.4 Å polymorph was grown by vacuum sublimation on $`a`$-SiO2 at 363 K. The Bragg-Brentano diffraction pattern indicated that the 2$`\mu `$m thick film contained mostly the 14.4 Å structure, with small amounts of 15.4 and 14.1 Å polymorphs. The 15.4 Å phase was removed using Gundlachs method  of dipping the film in ethanol. A new diffraction pattern confirmed this. The film was mechanically removed from the substrate and ground into a powder. The powder was dispersed on Scotch tape and remeasured in a transmission geometry on the Bruker D8 diffractometer. The powder diffraction pattern at room temperature is shown in Fig. 4.

Clearly, reflections other than $`\mathit{00}l`$ can be observed. The unit cell parameters were analyzed, while the fractional coordinates were not further refined. The pattern can be fitted with a mixture of two phases. The majority phase (91%) was found to have unit cell parameters which are listed in Table 2, and yields a $`d`$(001) of 14.37 Å. A minority phase could be indexed with the 14.1 Å single crystal unit cell.

## The 15.0 and 15.4 Å polymorphs: electron diffraction

Because the 15.0 and 15.4 Å polymorphs can only be grown for small film thickness, insufficient sample was available for X-ray powder diffraction. Here, we used electron diffraction (ED) to obtain structural information.

We performed electron diffraction experiments in a transmission geometry. ED has the advantage above X-ray based techniques, that the incident beam can be focussed. The scattering cross section is large, and can thus probe very small areas. In our ED experiments an electron beam with a diameter of 0.3 $`\mu `$m is used. Atomic force microscopy pictures of thin films show that films made at room temperature typically have a crystal size of 0.2 - 0.3 $`\mu `$m. Films grown at a higher temperature are more crystalline, and exhibit crystal sizes up to 1 $`\mu `$m. Electron diffraction offers thus the possibility to perform diffraction experiments on one single crystal area instead of a polycrystalline sample.

Samples for ED were prepared by evaporating a pentacene layer on a copper grid, which is covered with a carbon film. The pentacene layer of $``$100 nm, was evaporated on a substrate which was held at 345 K. When a single crystal area is located on the sample, the ED image exhibits spots instead of circles, as shown in Fig. 5. X-ray diffraction experiments showed strong preferential orientation with the \[00l\] axis. Therefore it is likely that the spot patterns observed with ED, in transmission, are generated by the (hk0) planes. From this diffraction pattern, the reciprocal lattice parameters $`a^{}`$, $`b^{}`$ and $`\gamma ^{}`$ can be determined. This measurement was calibrated by measuring a gold sample as reference. Various diffraction measurements, on different locations on the same sample, resulted in three different sets of $`𝐚^{}`$, $`𝐛^{}`$ and $`\gamma ^{}`$ values. We observed on an edge of the same sample also one $`𝐜^{}`$ value. The results are listed in Table 3. The reciprocal lattice data of the single crystal and the ED results calculated from Minakata et al.  have been added to this table. Note that the difference between $`𝐚^{}`$ and -$`𝐚^{}`$ or $`𝐛^{}`$ and -$`𝐛^{}`$ could not be observed. Therefore a $`\gamma ^{}`$ value of $`89^{}`$ can also be 91.

We observe all four polymorphs of pentacene on the same sample. In the first set of observed values (ED1, see Table 3) the $`𝐚^{}`$ and $`𝐛^{}`$ values correspond to the single crystal data. The $`\gamma ^{}`$ value, however, deviates beyond the measuring precision from the value determined with single crystal diffraction. We have no explanation for this difference and neglect it. The 14.4 Å phase was present, as an observed $`𝐜^{}`$ value (ED2) indicates the presence of this polymorph. The third set of parameters observed in our ED experiments (ED3) is in good agreement with the values observed by Minakata et al. However, their reported $`𝐜^{}`$ value was measured on a sample grown under the same conditions, but on a different substrate. Since we observed the nature of the substrate to be of crucial importance to the growth of a specific polymorph, we omit their reported value of $`𝐜^{}`$. ED4 in Table 3 lists a third set of $`𝐚^{}`$, $`𝐛^{}`$ and $`\gamma ^{}`$ values. These sets of data, ED3 and ED4, will belong to the 15.0 and 15.4 Å polymorphs.

In these experiments the electron beam was perpendicular to the substrate. By tilting the sample other reciprocal lattice vectors can be brought in diffraction condition. If sufficient hkl spots are identified, the unit cell can be constructed. However, the tilting may not change the small single crystalline area under study. Presently, tilting did affect the sample position, and we could not ascertain that the diffraction pattern belonged to the same polymorph. Furthermore, after a short exposure to the electron beam, the material suffered from radiation damage. Future modifications of the apparatus will allow to tilt the sample while keeping the same crystal in the beam.

## Charge transport properties of the 14.1 Å polymorph.

We have used space-charge-limited-current measurements on single crystals of pentacene to determine the hole mobility of the 14.1 Å polymorph. Single crystals were grown under an argon atmosphere as described earlier. Rectangular shaped crystals (platelets) were glued onto glass substrates using GE-varnish. Contacts were applied using a shadow mask. Stripes of 10 nm titanium and 40 nm gold were evaporated in a high vacuum environment. Distances between the stripes were 50 or 75 $`\mu `$m. Measurements were performed in the $`ab`$ plane. Platinum wires were connected to the stripes with silver epoxy. The epoxy was cured at 70C in air for 10 minutes. The crystals were exposed to air for approximately one hour before they were placed in vacuum. Samples were measured in darkness and a vacuum of 2 $``$ 10-7 mbar. As measuring device a Keithley 2410 high voltage sourcemeter was used. The $`J`$($`E`$) characteristics were measured using a pulsed staircase sweep with a pulsewidth of 0.3 sec.

The J(E) measurements can seen in Fig. 6. The results of these current-voltage measurements can be described using the standard semiconductor band model . We assume holes to be the majority carriers in the crystals. From analysis of the curves  we calculated the hole mobility, trap density, the energy of the trap level and the acceptor density: $`\mu `$ = 0.2 cm2/Vs, Nt = 2 $``$ 1013 cm-3, Et = 580 meV and Na 4 $``$ 1012 cm-3.

## Conclusion

Pentacene has been shown to crystallize in four different polymorphs. These different structures can be identified by their $`d`$(001) value, which is characteristic for the structure. Values of 14.1, 14.4, 15.0 and 15.4 Å have been observed. Single crystals commonly adopt the shortest $`d`$(001) spacing of 14.1 Å. All four polymorphs can be made as thin films. The growth of the different polymorphs as thin films was shown to depend strongly on the substrate, substrate temperature and film thickness. The 14.4 and 15.4 Å polymorphs appear to be induced by the substrate.

Temperature dependent X-ray diffraction measurements showed that the 14.1 and 14.4 Å phases are the most stable. The 15.0 and 15.4 Å structures are less stable and can be changed into 14.1 and 14.4 Å, respectively, at elevated temperatures or by exposing them to solvents. There is no indication of a structural phase transition in the 14.1 and 14.4 Å phases in the temperature range of 143 - 473 K.

Pentacene single crystals have been grown, both by vapour transport methods and from solution. The crystal structure that we report  agrees with the analysis of Holmes et al.  and Siegrist et al. , but is distinctly different from the data reported by Campbell et al. .

Pentacene is during crystal growth sensitive to both oxidation and hydrogenation, resulting in single crystals of dihydropentacene and pentacenequinone. The methylene and carbonyl groups are located at opposite sides of the middle ring, which seems the most reactive.

Powder diffraction experiments were used to obtain the unit cell parameters of the 14.4 Å polymorph. Electron diffraction experiments revealed for three polymorphs the $`𝐚^{}`$, $`𝐛^{}`$ and $`\gamma ^{}`$ values.

Using SCLC measurements we determined the mobility of the 14.1 Å polymorph of pentacene to be 0.2 cm2/Vs. Furthermore, these measurements show our single crystals to be very pure, having only 1013 traps cm-3.

## Acknowledgements

We acknowledge stimulating discussions with G. Wiegers. We thank H. Zandbergen for stimulating contributions for the electron diffraction results.