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# Into the future with GAIA

## 1. Structure and Evolution of the Milky Way

The final sentences of Ken Freeman’s influential 1987 review of ‘The Galactic Spheroid and Old Disk’ read: In this review, I have emphasized studies attempting to elucidate the present dynamical state of the Galaxy. This knowledge is needed before we can hope to proceed with any confidence to the next step: understanding the chain of events that occurred during the formation of the Galaxy. This next step is the main scientific goal of GAIA111The acronym has many interpretations, with Galactic Astrophysics through Imaging and Astrometry and Great Advance In Astrophysics amongst them., an astrophysics mission selected as Cornerstone 6 in the ESA science program (Perryman et al. 2001). A brief look into this future opportunity for Milky Way research is therefore particularly appropriate at this symposium in honor of Ken.

The Milky Way contains a complex mix of stars, planets, interstellar gas and dust, and dark matter. These components are distributed in age (reflecting their birth rate), in space (reflecting their birth places and subsequent motions), on orbits (determined by the gravitational force generated by their own mass), and in chemical element abundances (determined by the past history of star formation and gas accretion). To understand the formation, structure and evolution of our Galaxy therefore requires three complementary observational approaches: (i) a census of the contents of a large and representative part of the Galaxy; (ii) quantification of the present spatial structure, from distances; (iii) determination of the three-dimensional motions. This can be obtained from complementary astrometry, photometry, and radial velocities.

Astrometric measurements uniquely provide model-independent distances (trigonometic parallaxes) and transverse kinematics (proper motions). Multi-color photometry, with appropriate astrometric and astrophysical calibration, provides a measure of extinction, and hence, combined with astrometry, allows derivation of intrinsic luminosities, spatial distribution functions, and stellar chemical abundance and age information. Radial velocities complete the kinematic triad, allowing determination of gravitational forces, stellar orbits, and the distribution of invisible mass. Astrometry and limited photometry from HIPPARCOS, supplemented with ground-based radial velocities, provided this information for $``$$`10^5`$ stars in one small part of the Milky Way, the immediate Solar neighborhood. GAIA will provide a representative census of the entire Galaxy in one fell swoop, by repeatedly measuring the positions and multi-color brightness of all $`10^9`$ objects to $`V=20`$ mag, and radial velocities to $`V=17`$ mag (Table 1). The astrometric accuracies will be at the micro-arcsec ($`\mu `$as) level, and will provide distances to better than 10% well beyond the Galactic Center. Individual stellar motions will be measured even in M31. On-board detection will ensure that variable stars, supernovae, transient sources, micro-lensed events, and minor planets will all be observed and catalogued to $`V=20`$ mag.

## 2. Science with GAIA

The range of scientific topics which will be addressed by the GAIA data is vast, covering much of modern astrophysics, as well as Solar system studies and fundamental physics. A full description can be found in the ESA Concept and Technology Study, available on the GAIA website http://astro.estec.esa.nl/GAIA. Documents there contain references to the original work briefly summarized here, as well as details of the many other exciting scientific projects which GAIA will address, but which space precludes discussion of here.

### 2.1. The stellar halo of the Milky Way

The ESA Concept and Technology study identified many areas of Milky Way research where GAIA will make decisive contributions, including the structure of the Galactic bulge, the determination of the distribution of dark matter, the delineation of spiral structure, the internal dynamical structure of star forming regions and globular clusters, retracing the paths of run-away stars, etc. Here we focus on one such area: the key role of the stellar halo in distinguishing among competing galaxy formation scenarios. The recent review by Freeman & Bland-Hawthorn (2002) covers this topic in great depth.

The stellar halo contains only a small fraction of the total luminous mass of the Galaxy, but the kinematics and abundances of halo stars, globular clusters, and the dwarf satellites contain imprints of the formation of the entire Milky Way. The most metal-deficient stars, with \[Fe/H\] $`<3.5`$, represent a powerful tool to understand primordial abundances and the nature of the objects which produced the first heavy elements. The classical picture of inner monolithic collapse, combined with later accretion in the outer Galaxy, predicts a smooth distribution both in configuration and velocity space for our Solar neighborhood. The currently popular theories of hierarchical formation of structure propose that big galaxies are formed by mergers and accretion of smaller building blocks. These events leave signatures in the phase-space distribution of the stars that once formed those systems but are now part of the stellar halo.

In the hierarchical scenario, the current spatial distribution of stars in the inner halo should be fairly uniform, whereas strong clumping is expected in velocity space. This clumping reveals itself in the form of a large number of moving groups (several hundred in a 1 kpc3 volume centered on the Sun, if the whole stellar halo were built in this way) each having very small velocity dispersion. The required velocity accuracies to detect individual halo streams are less than a few km s-1, requiring measurement precision of order $`\mu `$as. A good way to find such streams is to use the space of adiabatic invariants. Here clumping should be stronger since all stars originating from the same progenitor have very similar integrals of motion, resulting in a superposition of the corresponding streams. In this way, Helmi et al. (1999) found evidence for one halo stream in the HIPPARCOS data, which must have resulted from an accretion about 12 Gyr ago. The future astrometric missions DIVA and FAME will find some additional streams, but it will take the GAIA accuracy, limiting magnitude, and radial velocities to reconstruct the entire set of merged satellites (Helmi & de Zeeuw 2000).

### 2.2. Stellar Astrophysics

GAIA will provide distances to an unprecedented 0.1% accuracy for $`7\times 10^5`$ stars out to a few hundred pc, and to 1% accuracy for a staggering $`2\times 10^7`$ stars up to a few kpc. Distances to better than 10% will reach beyond 10 kpc, and will cover a significant fraction of our Galaxy, including the Galactic Center, spiral arms, the halo, and the bulge, and—for the brightest stars—to the nearest satellites. With the parallel determination of extinction/reddening and metallicities by means of multi-band photometry and spectroscopy, this will provide an extended basis for reading in situ stellar and galactic evolution. All parts of the Hertzsprung–Russell diagram will be comprehensively calibrated, from pre-main sequence stars to white dwarfs and all transient phases; all possible masses, from brown dwarfs to the most massive O stars; all types of variable stars; all possible types of binary systems down to brown dwarf and planetary systems; and all standard distance indicators (pulsating stars, cluster sequences, supergiants, central stars of planetary nebulae, etc.). This extensive amount of accurate data will stimulate a revolution in the exploration of stellar and Galactic formation and evolution, and the determination of the cosmic distance scale.

The GAIA large-scale photometric survey will have significant intrinsic scientific value for stellar astrophysics, providing $`2\times 10^7`$ variable stars of nearly all types, including detached eclipsing binaries, contact or semi-contact binaries, and pulsating stars. The pulsating stars include key distance calibrators such as Cepheids and RR Lyrae stars and long-period variables. Existing samples are incomplete already at magnitudes as bright as $`V10`$ mag. The GAIA samples to $`V=20`$ will be sufficiently large ($`10^4`$ Cepheids, and $`10^5`$ RR Lyrae’s) to calibrate period-luminosity relationships across a wide range of stellar parameters, including metallicity. A systematic variability search in the entire GAIA survey will also reveal stars in short-lived but key stages of stellar evolution, such as the helium core flash and the helium shell thermal pulses and flashes. Prompt processing will identify many targets for follow-up ground-based studies.

### 2.3. The star formation history of the Galaxy

A central element of the GAIA mission is the determination of the evolution of the star formation rate, and the cumulative numbers of stars formed, of the bulge, inner disk, Solar neighborhood, outer disk and halo of our Galaxy. This information, together with the kinematic information from GAIA, and complementary chemical abundance information, again primarily from GAIA, provides the full evolutionary history of the Galaxy.

### 2.4. Binaries and extrasolar planets

Many of the $`10^9`$ stars to be observed by GAIA are not single. A key constraint on double and multiple star formation is the distribution of mass-ratios $`q`$. For wide pairs ($`>0.^{\prime \prime }5`$) this follows from the distribution of magnitude differences $`\mathrm{\Delta }m`$. GAIA will provide a photometric determination of the $`q`$-distribution down to $`q0.1`$, covering the expected maximum around $`q0.2`$. Furthermore, the large numbers of astrometric orbits will allow derivation of the important statistics of the very smallest (brown dwarf) masses as well as the detailed distribution of orbital eccentricities.

GAIA is very sensitive to non-linear proper motions. A large fraction of all astrometric binaries with periods from 0.03–30 years will be recognized by their poor fit to a standard single-star model. Most will be unresolved, with very unequal mass-ratios and/or magnitudes, but in many cases a photocenter orbit can be determined. For this period range, the absolute and relative binary frequency can be established, with the important possibility of exploring variations with age and place of formation in the Galaxy. Some $`10^7`$ binaries closer than 250 pc will be detected, with much larger numbers still detectable out to 1 kpc and beyond. This binary census will also cover essentially the entire (period, $`\mathrm{\Delta }m`$) diagram: the classical ‘area of ignorance’ between the short-period spectroscopic binaries and the long-period visual binaries will finally be mapped.

GAIA’s potential for planet detection was assessed by simulating observations of a homogeneous set of extra-solar planetary systems, to establish the expected sensitivity to the presence of planets and the potential for accurate estimation of orbital parameters, as a function of semi-major axis, period, and eccentricity, and the distance from the Sun. These simulations put the number of astrometric detections of Jupiter-mass planets somewhere between 10,000–50,000, depending on details of the detection and orbital distribution hypotheses. Essentially all Jupiter-mass planets within 50 pc and with periods between 1.5–9 yr will be discovered by GAIA. Photometric detections of planetary transits will also be a natural product of the GAIA photometry.

### 2.5. Solar System

Solar system objects present a challenge to GAIA because of their significant proper motions, but they promise a rich scientific reward. The minor bodies provide a record of the conditions in the proto-Solar nebula, and their properties therefore shed light on the formation of planetary systems. Discovery and orbital determination of near-Earth objects is a subject of high public interest.

GAIA will detect between $`10^5`$ and $`10^6`$ new asteroids, and obtain precise orbits for them. They will include all near-Earth objects with diameters larger than about 1 km, as well as Trojans of Mars and Venus. The mission will also provide an all-sky search for Kuiper Belt Objects, which should produce about 300 brighter than $`V=20`$ mag. These are remnants of the pre-Solar nebula, and form the closest link with disks around young stellar objects.

### 2.6. Extragalactic astrophysics

GAIA will make unique contributions to extragalactic astronomy, including the structure, dynamics and stellar populations in the Magellanic Clouds and other Galactic satellites, and in M31 and M33, with consequences comparable to those summarized above for the Milky Way. The faint magnitude limit and all-sky coverage allows derivation of the space motions of Local Group galaxies, and studies of large numbers of supernovae, galactic nuclei, and quasars.

Local Group. The orbits of galaxies are a result of mildly non-linear gravitational interactions, which link the present positions and velocities to the cosmological initial conditions. Non-gravitational (hydrodynamic) or strongly non-linear gravitational interactions (collisions, mergers) are sometimes significant. It will be possible to determine reliable three-dimensional orbits for a significant sample of galaxies in the Local Group, in a region large and massive enough to provide a fair probe of the mass density in the Universe. This provides direct constraints on the initial spectrum of perturbations in the early Universe, on the global cosmological density parameter $`\mathrm{\Omega }`$, and on the relative distributions of mass and light on length scales up to 1 Mpc.

Galaxies. GAIA will provide multi-color photometry with $``$$`0.^{\prime \prime }3`$ spatial resolution for all sufficiently high-surface-brightness galaxies. This allows statistical analysis of the photometric structure and color distribution of the central regions of a complete, magnitude-limited sample of many tens of thousands of galaxies with a resolution not achievable from the ground, and study of the large-scale structure of the local Universe. This naturally complements available redshift surveys, and the deeper pencil-beam studies with large telescopes.

Supernovae. GAIA will detect all point-like objects brighter than $`V=20`$ mag, so that supernovae can be detected to a modulus of $`mM39`$ mag, i.e., to $`z0.1`$. Simulations show that GAIA will detect over $`\mathrm{100\hspace{0.17em}000}`$ supernovae of all types. Of these, the most useful as cosmological-scale distance indicators are the Type Ia supernovae, whose light curves are very accurate distance indicators. Rapid detection of such transient sources will allow detailed ground-based determination of lightcurves and redshifts.

Quasars. The astrometry to $`V=20`$ mag will provide a census of $`\mathrm{500\hspace{0.17em}000}`$ quasars. The mean surface density of $`25\mathrm{deg}^2`$ at intermediate to high Galactic latitudes will provide the direct link between the GAIA astrometric reference system and an inertial frame. GAIA will be sensitive to multiply-imaged quasars with separations as small as $`0.^{\prime \prime }2`$, which is the regime where most of the lensing due to individual galaxies is expected. Photometric variability of such systems will allow accurate measurement of the Hubble constant, and the entire quasar sample will provide constraints on the cosmological parameters $`\mathrm{\Omega }`$ and $`\mathrm{\Lambda }_0`$.

### 2.7. Fundamental Physics

The dominant relativistic effect in the GAIA measurements is gravitational light bending. Accurate measurement of the parameter $`\gamma `$ of the Parametrized Post-Newtonian (PPN) formulation of gravitational theories is of key importance in fundamental physics. Light deflection depends on both the time-space and space-space components of the metric tensor, and has been observed on distance scales of $`10^910^{21}`$ m, and on mass scales from $`110^{13}M_{}`$, the upper ranges determined from the gravitational lensing of quasars. GAIA will extend these domains by two orders of magnitude in length, and six orders of magnitude in mass. GAIA will provide a precision of about $`5\times 10^7`$ for $`\gamma `$, based on multiple observations of $`10^7`$ stars with $`V<13`$ mag at wide angles from the Sun, with individual measurement accuracies better than $`10\mu `$as. This accuracy is close to the values predicted by theories that assume the Universe started with a strong scalar component, which then relaxed to the general relativistic value with time.

Other possibilities include determination of the solar oblateness, from analysis of suitable asteroid orbits, and limiting any gravitational wave backgrounds, from determinations of coherent jitter in the quasar reference frame. Gravitational waves passing over the telescope will cause a time-varying shift in the apparent position of a source; i.e., the waves cause apparent proper motions which are coherent across the whole sky. GAIA could set, in the $`10^{12}<f<10^{10}`$ Hz band, the best upper limit on $`\mathrm{\Omega }_{\mathrm{gw}}`$.

## 3. The payload

The proposed GAIA design has arisen from requirements on astrometric precision (10 $`\mu `$as at 15 mag), completeness to $`V=20`$ mag, the acquisition of radial velocities, the provision of accurate multi-color photometry for astrophysical diagnostics, and the need for on-board object detection. The result is a continuously scanning spacecraft, accurately measuring one-dimensional coordinates along great circles, and in two simultaneous fields of view, separated by a well-defined and well-known ‘basic’ angle. These one-dimensional coordinates are then converted into the astrometric parameters in a global data analysis which will provide distances and proper motions, as well as information on double and multiple systems, photometry, variability, metric, planetary systems, etc. The payload is based on a large CCD focal plane assembly, with passive thermal control, and a natural short-term (3 hour) instrument stability due to a sunshield, the selected orbit, and a robust payload design (Figure 1).

The telescopes are of moderate size, with no specific design or manufacturing complexity. The system fits within a dual-launch Ariane 5 configuration, without deployment of any payload elements. A ‘Lissajous’ orbit at the outer Lagrange point L2 is the preferred operational orbit, from where an average of 1 Mbit of data per second is returned to a single ground station throughout the planned five-year mission. The 10 $`\mu `$as accuracy target has been shown to be realistic through a comprehensive accuracy assessment program; this remarkable accuracy is possible partly by virtue of the (unusual) instrumental self-calibration achieved through the data analysis on-ground. This ensures that final accuracies essentially reflect the photon noise limit for localisation accuracy: this demanding challenge was proven deliverable by HIPPARCOS. Figure 2 illustrates the expected accuracy as a function of magnitude (Perryman et al. 2001).

## 4. Data analysis

The total amount of (compressed) science data generated in the course of a five-year mission is about $`2\times 10^{13}`$ bytes (20 TB). Most of this consists of CCD raw or binned pixel values with associated identification tags. The data analysis aims to ‘explain’ these values in terms of astronomical objects and their characteristics by iteratively adjusting the object, attitude and instrument models until a satisfactory agreement is found between predicted and observed data. This will require expert knowledge from several different fields of astronomy, mathematics and computer science to be merged in a single efficient system, including

* physical modeling of the observations in terms of detectors, optics, satellite attitude and the astrometric and photometric characteristics of the objects, including a fully general-relativistic treatment consistent to the 1 $`\mu `$as level;
* accurate geometric and photometric calibration of the instruments, including the celestial orientation (attitude) of the instrument axes;
* efficient procedures for generating and maintaining software, and for the management, processing and dissemination of data.

The ESA Concept and Technology Study considered neural network techniques and object-orientated data structures, and included a detailed assessment of the storage, computational processing and algorithmic demands of the resulting satellite data stream. The simulations have supplied confidence that, while challenging, efficient data reduction is feasible, assuming conservative projections of recent developments in storage devices and computational capabilities.

## 5. The GAIA Observatory

The GAIA study demonstrated that star selection can be effectively undertaken autonomously on-board, which has the fundamental advantage that GAIA science targets will be complete and unbiased. It also eliminates the need for a complex and costly pre-launch program of observation definition: science operations associated with the mission will also be simplified correspondingly.

Every one of the 109 GAIA targets will be observed typically 100 times, each time in a complete set of photometric filters, and a large fraction also with a radial velocity spectrograph. The spatial resolution exceeds that available in ground-based surveys. Source detection happens on-board at each focal-plane transit, so that variable and transient sources are detected. All these complementary datasets, in addition to the superb positional and kinematic accuracy which is derivable from their sum, make GAIA an optimal observatory mission: every observable source will be observed every time it crosses the focal plane.

These data allow studies from asteroids to distant supernovae, from planets to galaxies, and naturally interest almost the entire astronomical community. For this reason, GAIA will be an open observatory mission, directly making available its rich scientific resource to the sponsoring communities. The scale of the GAIA data is such that many analyses can be undertaken during operations, while others will await final data reduction. The GAIA observatory will provide exciting scientific data to a very wide community, beginning with the first photometric observations, and rapidly increasing until the fully reduced GAIA data become available. The resulting analyses will provide a vast scientific legacy.

It is useful to compare GAIA with other astrometric missions. NASA’s SIM, to be launched around 2009, will be an interferometer, ideal for precise measurements of a small number of carefully pre-selected targets of specific scientific interest, focussed towards searches for low-mass planets around a few nearby stars, calibration of the distance scale, and detailed studies of known micro-lensing events. FAME, a NASA MIDEX mission, and DIVA, a small German satellite, both to be launched in 2004, are essentially successors to HIPPARCOS, with an extension of limiting sensitivity, sample size and accuracy by a factor of order 100 in each. They will both substantially improve calibration of the distance scale and the main phases of stellar evolutionary astrophysics, and map the Solar neighborhood to much improved precision. GAIA exceeds these two missions in scale by a further factor of order 100, allowing study of the entire Galaxy, and only GAIA will provide photometric and radial velocity measurements as crucial astrophysical diagnostics.

## 6. Concluding remarks

GAIA will make it possible to create an extremely precise three-dimensional map of a representative sample of stars throughout our Galaxy and beyond. In the process, by combining positional data with complementary radial velocities, GAIA will map the stellar space motions. Through comprehensive photometric classification, GAIA will provide the detailed physical properties of each star observed: characterizing their luminosity, temperature, gravity, and elemental composition. This massive multi-parameter stellar census will provide the basic observational data to quantify the origin, structure, and evolutionary history of our Galaxy. The result is also of key significance for quantitative studies of the high-redshift Universe: a well-studied nearby template underpins analysis of unresolved galaxies with other facilities, and at other wavelengths.

While challenging, the entire GAIA design is within the projected state-of-the-art: the satellite is being developed in time for launch in 2010. By combining current technology with the demonstrated HIPPARCOS measurement principles, GAIA will deliver an orders of magnitude improvement in our knowledge of our Galaxy, in terms of accuracy, number of objects, and limiting magnitude. With this schedule, a complete stereoscopic map of our Galaxy will be available within 15 years. The successful completion of this program will characterize the structure and evolution of stars and our Galaxy in a manner completely impossible using any other methods, and nearly inconceivable as recently as the time of Ken’s 1987 review. This is an excellent prospect to look forward to when considering Ken’s 75th birthday celebration!

#### Acknowledgments.

It is a pleasure to thank Ken and Margaret for many years of stimulating friendship, and to thank Gary Da Costa for his excellent organization, choice of conference venue, and patience with a delinquent author. This paper owes much to contributions by the GAIA Science Advisory Group, notably Michael Perryman and Gerry Gilmore.

## References

Freeman K.C., 1987, ARA&A, 25, 603–632

Freeman K.C., Bland-Hawthorn J., 2002, ARA&A, in press

Helmi A., de Zeeuw P.T., 2000, MNRAS, 319, 657

Helmi A., White S.D.M., de Zeeuw P.T., Zhao H.S., 1999, Nature, 402, 53

Perryman M.A.C., et al. 2001, A&A, 369, 339


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# Dewetting of Glassy Polymer Films

## Abstract

Dynamics and morphology of hole growth in a film of power hardening viscoplastic solid (yield stress $``$ \[strain-rate\]n) is investigated. At short-times the growth is exponential and depends on the initial hole size. At long-times, for $`n>\frac{1}{3}`$, the growth is exponential with a different exponent. However, for $`n<\frac{1}{3}`$, the hole growth slows; the hole radius approaches an asymptotic value as $`t\mathrm{}`$. The rim shape is highly asymmetric, the height of which has a power law dependence on the hole radius (exponent close to unity for $`0.25<n<0.4`$). The above results explain recent intriguing experiments of Reiter, Phys. Rev. Lett., 87, 186101 (2001).

Dewetting of largely glassy polymer films below or near their glass transition temperature is a highly intriguing phenomenonReiter2001  in that the usual mechanisms of shape change such as viscous fluid flow, surface diffusion, evaporation/condensation are not dominantReiter2001 . Thus, near glass transition temperature, solid-like plastic yielding and resulting flow of the glassy polymer appears to be the only mechanism of dissipation during dewetting.

Indeed, ReiterReiter2001  recently observed the growth of holes in glassy polymer films with features very unlike those predicted/observed in purely viscousRedon1991 ; Oron1997  films. The key features of the experiments are (i) the radius of the hole increases with time in an exponential manner (short time behaviour) (ii) the growth slows down considerably at long times, to the extent even of nearly stoppingReiter2002  (iii) the hole grows with a highly unsymmetric raised rim (iv) the height of the rim is nearly linearly dependent on the radius of the hole.

In this Letter, we investigate the role of plastic yielding and resulting flow on the dynamics and morphology of growing holes in glassy polymer films. Our model is based on two physical premises: (i) the dewetting hole growth is driven by capillary forces, and (ii) the polymeric film, near its glass transition temperature, behaves as a strain-rate hardening viscoplastic solidCrist1993 , i. e., the yield stress $``$ (effective strain-rate)n, where $`n`$ is the strain-rate hardening exponent (henceforth called simply as “hardening exponent”). The analysis uncovers a rich variety of regimes of hole growth some of which correspond to the experiments of ReiterReiter2001 .

The model consists of a flat film of initial thickness $`h_o`$ with a hole of radius $`R_o`$(see FIG. 1); we focus on the growth of an existing hole rather than the mechanism of initial hole formation. As the hole grows, the radius increases to $`r_o`$ and the thickness becomes inhomogeneous. The aim of the analysis is to obtain the rate of the hole growth and the profile of the film including the height of the rim.

Capillary forces are taken to be responsible for hole growth. As the hole grows there is a net reduction in interfacial energy, the rate of which is given by

$`\dot{E}_s=2\pi |S|r_o\dot{r}_o`$ (1)
with $`|S|=|\gamma _{sa}\gamma _{sf}\gamma _{fa}|`$ is the spreading coefficient, where $`\gamma _{sf}`$ is the interfacial energy between the film and the substrate, $`\gamma _{sa}`$ is the surface energy of the substrate in contact with air and $`\gamma _{fa}`$ is the surface energy of the film in contact with air. As the film grows, the height $`h(r_o)`$ of the rim increases and so does the surface area of the cylindrical surface of the hole. The rate of increase in the surface energy is given by

$`\dot{E}_f=2\pi \gamma _{fa}\left(h(r_o)+h^{}(r_o)r_o\right)\dot{r}_o.`$ (2)
(We neglect the rate of increase of surface area on the top surface of the film, and this slightly overestimates the hole growth velocity). Applying principle of conservation of energy, we get

$`\dot{E}_s=\dot{E}_f+D_p`$ (3)
where $`D_p`$ is the rate of plastic dissipation in the deforming film.

The plastic dissipation $`D_p`$ (see final expression (14) below) is obtained as follows. It is assumed that the film can slip freely on the substrate, i. e., the shear stress at the film substrate interface vanishes – this assumption is justified by the fact that the filmReiter2001  is deposited on a monolayer of PDMS. Neglecting inertial effects, dynamics provides a relation between the stress components (a plane stress assumption with a vanishing component of stress normal to the substrate ($`\sigma _{zz}=0`$) is made)

$`{\displaystyle \frac{\text{d}\sigma _{rr}}{\text{d}r}}+{\displaystyle \frac{\sigma _{rr}\sigma _{\theta \theta }}{r}}=0.`$ (4)
where $`\sigma _{rr}`$ and $`\sigma _{\theta \theta }`$ are the radial and circumstantial components of the Cauchy stress tensor. Nonlinear kinematics of large deformation is treated; the radial coordinate of the undeformed film is described by $`R`$ and that of the deformed film by $`r`$. The deformation map can be expressed as $`r=r(R,t)`$ i. e., a point which was at a radial distance of $`R`$ at the initial instance will move to a radial position $`r`$ at time $`t`$. In particular, $`r_o(t)=r(R_o,t)`$ is the radius of the deformed hole. The radial velocity is the time derivative of $`r`$ defined as $`v=r(R,t)/t=\dot{r}(R,t)`$; the radial velocity of expansion of the hole is denoted as $`\dot{r_o}=\dot{r}(R_o,t)`$. The stretching rates $`ϵ_{rr}`$, $`ϵ_{\theta \theta }`$ and $`ϵ_{zz}`$ are expressed in terms of the velocity field as

$`ϵ_{rr}={\displaystyle \frac{v}{r}},ϵ_{\theta \theta }={\displaystyle \frac{v}{r}},ϵ_{zz}=(ϵ_{rr}+ϵ_{\theta \theta }).`$ (5)
Evidently, the kinematics ensures that the resulting deformation is incompressible.

We neglect elastic strains and treat the deformation as completely plastic. The polymeric material is taken to be a rate-sensitive plastic material (viscoplastic material) with power law strain rate hardening. The effective stress and the effective plastic strain rate at a material point are related by

$`\sigma _e=k\epsilon ^n`$ (6)
where $`\sigma _e=\sqrt{\frac{3}{2}s_{ij}s_{ij}}`$ with $`s_{ij}=\sigma _{ij}\frac{1}{3}\sigma _{kk}\delta _{ij}`$ is the deviatoric stress tensor, $`\epsilon `$ is the effective plastic strain rate defined as $`\epsilon =\sqrt{\frac{2}{3}ϵ_{ij}ϵ_{ij}}`$, $`k`$ is a material constant and $`n`$ is the hardening exponent. The polymeric material is assumed to obey an associative flow ruleKhan1995 , i. e.,

$`ϵ_{ij}=\lambda s_{ij}`$ (7)
where $`\lambda `$ is a number; the associative rule ensures that the plastic strain rate is normal to the yield surface. Relations (4), (5), (6) and (7) provide a complete set of equations for investigating hole growth in the polymeric film.

Expression (7) can be used to express the nonvanishing stresses in terms of the stretching rates as

$`\sigma _{rr}={\displaystyle \frac{2ϵ_{rr}+ϵ_{\theta \theta }}{\lambda }},\sigma _{rr}\sigma _{\theta \theta }`$ $`=`$ $`{\displaystyle \frac{ϵ_{rr}ϵ_{\theta \theta }}{\lambda }}.`$ (8)
These expressions can be substituted in (6) to find $`\frac{1}{\lambda }=\frac{2}{3}k\epsilon ^{n1}`$ – the stresses are thus expressed completely in terms of the stretching rates.

On substituting the above information into the equilibrium equation (4), we get,

$`{\displaystyle \frac{\text{d}}{\text{d}r}}\left(\epsilon ^{n1}\left(2{\displaystyle \frac{\text{d}v}{\text{d}r}}+{\displaystyle \frac{v}{r}}\right)\right)+\epsilon ^{n1}{\displaystyle \frac{1}{r}}\left({\displaystyle \frac{\text{d}v}{\text{d}r}}{\displaystyle \frac{v}{r}}\right)=0,`$ (9)
where

$`\epsilon =\sqrt{{\displaystyle \frac{2}{3}}\left[\left({\displaystyle \frac{\text{d}v}{\text{d}r}}\right)^2+\left({\displaystyle \frac{v}{r}}\right)^2+\left({\displaystyle \frac{\text{d}v}{\text{d}r}}+{\displaystyle \frac{v}{r}}\right)^2\right]}.`$ (10)
The solution of (9) provides an expression for the radial velocity

$`v(r)=\dot{r}=\dot{r_o}\left({\displaystyle \frac{r}{r_o}}\right)^{\frac{1+n}{2n}}.`$ (11)
This equation can be used to obtain an expression for the thickness profile of the film

$`h(r,t)=h_o\left({\displaystyle \frac{r}{R}}\right)^{\frac{1n}{2n}},R=\left(r^{\frac{1+3n}{2n}}r_o^{\frac{1+3n}{2n}}+R_o^{\frac{1+3n}{2n}}\right)^{\frac{2n}{1+3n}}.`$
(12)
To calculate the plastic dissipation, we substitute all the relevant quantities into the relation

$`D_p=2\pi {\displaystyle _{r_o}^{\mathrm{}}}k\epsilon ^{n+1}h(r)r\text{d}r`$ (13)
to obtain

$`D_p=2\pi \alpha kh_or_o^2\left({\displaystyle \frac{\dot{r_o}}{r_o}}\right)^{n+1}F_n\left({\displaystyle \frac{r_o}{R_o}}\right)`$ (14)
with

$`\alpha `$ $`=`$ $`2(3)^{\frac{1+n}{2}}(1+3n^2)^{\frac{n1}{2}}n^n,`$
$`F_n\left(x\right)`$ $`=`$ $`{}_{2}{}^{}F_{1}^{}\left[\frac{1n}{1+3n},\frac{1+3n^2}{1+3n};\frac{2+3n+3n^2}{1+3n};\left(1x^{\frac{1+3n}{2n}}\right)\right],`$
where $`{}_{2}{}^{}F_{1}^{}`$ is the hypergeometric function.

Using (1), (2) and (14) in (3), the rate of hole growth is obtained as

$`{\displaystyle \frac{\dot{r_o}}{R_o}}={\displaystyle \frac{1}{t_o}}\left(1\beta \left({\displaystyle \frac{r_o}{R_o}}\right)^{\frac{13n}{2n}}\right)^{\frac{1}{n}}\left(F_n\left({\displaystyle \frac{r_o}{R_o}}\right)\right)^{\frac{1}{n}}{\displaystyle \frac{r_o}{R_o}}`$
(15)
where $`t_o`$ is an intrinsic time constant of the film/substrate system defined as

$`t_o=\sqrt[n]{{\displaystyle \frac{\alpha kh_o}{|S|}}},`$ (16)
and

$`\beta ={\displaystyle \frac{1+n}{2n}}{\displaystyle \frac{\gamma _{fa}}{|S|}}{\displaystyle \frac{h_o}{R_o}}.`$ (17)
The rate of hole growth is controlled by two parameters $`\beta `$ which is a measure of capillary forces, and $`n`$ which is the strain-rate hardening exponent.

The solution to (Dewetting of Glassy Polymer Films) can be investigated analytically in two limits, $`tt_o`$ and $`tt_o`$. In the short-time limit $`(tt_o)`$, (Dewetting of Glassy Polymer Films) reduces to

$`{\displaystyle \frac{\dot{r_o}}{R_o}}{\displaystyle \frac{1}{t_o}}\left(1\beta \right){\displaystyle \frac{r_o}{R_o}}`$ (18)
since $`F_n(1)=1`$; thus the hole growth is exponential for short times. It is clear that for the hole to grow the parameter $`\beta `$ must be smaller than unity which provides a condition on the initial radius of the hole that allows for hole growth, i. e., $`\beta <1`$ implies

$`R_o>R_c={\displaystyle \frac{1+n}{2n}}{\displaystyle \frac{\gamma _{fa}}{|S|}}h_o`$ (19)
where $`R_c`$ is the critical radius for hole growth $`(\beta =R_c/R_o)`$. If the initial radius of the hole is less than $`R_c`$, the hole does not grow. As in a fluid film, the analysis for critical hole radius is most relevant when the film is sufficiently thick to ignore the excess intermolecular interactions.

The long-time behaviour $`(tt_o)`$ of the film is investigated in two different regimes of $`n`$. First, when $`n>\frac{1}{3}`$, the rate of growth (Dewetting of Glassy Polymer Films) for $`tt_o`$ reduces to

$`{\displaystyle \frac{\dot{r_o}}{R_o}}{\displaystyle \frac{L_n}{t_o}}{\displaystyle \frac{r_o}{R_o}}`$ (20)
$`(L_n=lim_x\mathrm{}F_n(x)^{\frac{1}{n}})`$ i. e., the growth continues to be exponential but with a different exponent $`L_n/t_o`$. A plot of $`L_n`$ as a function of $`n`$ is shown in FIG. 2. Thus, although the short time exponent depends on the initial radius $`R_o`$ of the hole (through $`\beta `$), the long time behaviour is independent of the initial size of the hole. Moreover, if the critical radius is small $`(R_ch_o)`$, then the long time growth rate of small unstable holes $`(\beta 1)`$ slows down compared to the initial growth rate $`L_n<(1\beta )`$.

When $`n<\frac{1}{3}`$, the long-time behaviour is very different from the above case. Indeed, the hole radius does not become indefinitely large, but attains a asymptotic value $`r_m`$ given by

$`r_m=\beta ^{\frac{2n}{13n}}R_o`$ (21)
A straightforward analysis shows that the approach of $`r_o`$ towards $`r_m`$ is governed by

$`{\displaystyle \frac{\dot{\overline{\mathrm{\Delta }r_o}}}{r_m}}{\displaystyle \frac{1}{t_o}}\left({\displaystyle \frac{13n}{2nF_n(r_m/R_o)}}\right)^{\frac{1}{n}}\left({\displaystyle \frac{\mathrm{\Delta }r_o}{r_m}}\right)^{\frac{1}{n}}`$ (22)
where $`\mathrm{\Delta }r_o=r_mr_o`$. Thus, $`r_o`$ approaches $`r_m`$ at a power law rate governed by the reciprocal of the hardening exponent, $`1/n`$.

The complete solution for (Dewetting of Glassy Polymer Films) for various combinations of $`n`$ and $`\beta `$ are shown in FIG. 3. All the features noted in the asymptotic analysis are reproduced. It is clear that for a given value of $`\beta `$ the rate of growth is larger when $`n`$ is larger, and for a given $`n`$, the rate of growth is larger when $`\beta `$ is smaller.

The time evolution of the film is also of interest; for $`rr_o`$, an asymptotic expression for the increase in the thickness of the film can be obtained (from (12)) as

$`\mathrm{\Delta }h(r,t)={\displaystyle \frac{(1n)}{(1+3n)}}{\displaystyle \frac{(r_o(t)^{\frac{1+3n}{2n}}R_o^{\frac{1+3n}{2n}})}{r^{\frac{1+3n}{2n}}}},(rr_o)`$ (23)
FIG. 4 shows snapshots of film profiles for two different values of $`n`$ for various times. A 3D view of the film profile is included in FIG. 5 for visualistion.

Another quantity, important from the experimental point of view, is the dependence of the height of the rim on its radius. From (12), it is evident that

$`{\displaystyle \frac{h(r_o)}{h_o}}=\left({\displaystyle \frac{r_o}{R_o}}\right)^{\frac{1n}{2n}}`$ (24)
which is, in general, a power law. However, if $`n`$ is close to $`1/3`$, the exponent is approximately unity. In fact, when $`n=0.25`$, $`h(r_o)r_o^{1.5}`$ and if $`n=0.4`$, then $`h(r_o)r_o^{0.75}`$ which implies that the relationship between the height of the rim and the radius of the hole is nearly linear in this regime.

The main conclusions of this Letter are summarised as follows: (i) There is a critical value for the initial size of the hole. If the size of the hole is larger than this value, the hole grows. (ii) The short time growth velocity of the hole is exponential and depends on the initial size of the hole. (iii) The long time growth velocity of the hole depends on the strain-rate hardening exponent $`n`$. When $`n>\frac{1}{3}`$, the hole radius grows exponentially with time with a rate of growth that does not depend on the initial size of the hole. For $`n<\frac{1}{3}`$, the hole growth slows down and the radius of the hole attains an asymptotic value $`r_m`$ that depends on the initial size of the hole. (iv) The height of the rim is approximately linearly related to the radius of the hole when $`0.25<n<0.4`$.

The recent observations of ReiterReiter2001  on hole growth in polystyrene films near glass transition temperature can be explained by the above theoretical results, supporting the premise that the hole growth in solid polymer films near $`T_g`$ is governed largely by yielding and subsequent plastic flow which provides the dominant dissipative mechanism. The theory also predicts a rich variety of growth behaviours which may help in the design and interpretation of new controlled experiments. Our theory for plastically deforming solids together with other recent theories of hole growth in viscoelastic fluidsSapid1996 ; Brochard-Wyart1997 ; Jacobs1998 ; Herminghaus2002  and shear thinning viscous fluidsSaulnier2002  provide complimentary models of dewetting over a wide range of temperatures from below $`T_g`$ to well above $`T_g`$.

Stimulating discussions with G. Reiter are gratefully acknowledged. This work was partially supported by Department of Science and Technology, and Samtel Color Ltd.


text:
# Insights into molecular conduction from I-V asymmetry

\[

## Abstract

We investigate the origin of asymmetry in the measured current-voltage (I-V) characteristics of molecules with no inherent spatial asymmetry. We establish that such molecules can exhibit asymmetric I-V characteristics due to unequal coupling with the contacts. In contrast with spatially asymmetric molecules, conduction takes place through essentially the same level in both bias directions. The asymmetry arises from a subtle difference in the charging effects, which can only be captured in a self-consistent model for molecular conduction. For HOMO-based conduction, the current is smaller for positive voltage on the stronger contact, while for LUMO conduction, the sense of asymmetry is switched.

\]

Future electronic devices are quite likely to incorporate molecular components, motivated by their size, mechanical flexibility and chemical tunability. This vision is nearing reality with the capacity to self-assemble, functionalize, and reproducibly measure the current-voltage (I-V) characteristics of small groups of molecules. Molecular I-Vs have revealed a wide range of conductance properties, from metallic conduction in carbon nanotubes  and quantum point contacts , to semiconducting behavior in DNA  and conjugated aromatic thiols , and insulating behavior in alkyl thiol chains . Interesting device characteristics such as rectification , switching  and transistor action  have also been reported.

The classic paradigm for asymmetry in molecular I-V measurements is the Aviram-Ratner diode, consisting of a semi-insulating molecular species bridging an electron donor-acceptor pair . A positive bias on the contact at the donor end brings the energy levels on the donor and acceptor sites into resonance, while the opposite bias moves the system away from resonance, leading to a strongly asymmetric I-V characteristic . Spatial asymmetry in the molecule is essential in generating the I-V asymmetry, causing the energy levels, the electrostatic potential and electron wavefunctions to be quite different for positive and negative voltages .

In this paper, we address an I-V asymmetry experimentally observed for spatially symmetric molecules  that is qualitatively different from and weaker than the rectification in spatially asymmetric molecules. The molecular I-V curves seen for these systems start off being symmetric, but pick up a weak, reversible asymmetry as the contacts are manipulated (Fig. 1). In contrast to spatially asymmetric molecules, conduction in these molecules at opposite voltages occur through essentially the same molecular levels with very similar wave functions. We show that the origin of the observed asymmetry is nontrivial, involving self-consistent shifts in the energy levels due to charging effects. Asymmetry in charging arises due to unequal coupling with the contacts, and can be present in conduction measurements performed with a break junction , an STM tip  or an evaporated gold contact . Remarkably, the sense of the asymmetry depends crucially on whether the conducting level is HOMO or LUMO. We establish that  for a spatially symmetric molecule the current is lower for positive bias on the stronger contact if conduction is through a HOMO level, and higher if conduction is through a LUMO level.

Although ab-initio calculations exist for molecular conduction , there is uncertainty about the position of the Fermi level even in idealized metal-molecular heterostructures. This uncertainty translates into a corresponding ambiguity in the conductance gap in molecular I-Vs, as well as the nature of the conducting orbitals. For phenyl dithiol (PDT) and its derivative molecules coupled to gold (111) contacts, the Fermi level has variously been suggested to be mid-gap , closer to the HOMO level , or closer to the LUMO . Although all these models predict similar symmetric I-Vs, the sense of the I-V asymmetry for asymmetric contacts pins down the nature of the conducting orbital rather restrictively; for instance, the I-V asymmetry measured for PDT with an STM tip  indicates HOMO-based conduction, as we show later.

Non self-consistent description of molecular conduction. An isolated molecule has discrete molecular levels, that are broadened upon coupling with contacts into a continuous density of states (DOS) due to hybridization with the metal wave functions. For molecules like PDT the broadening is weak enough that the DOS shows a clear HOMO-LUMO gap (HLG). The difference in the work functions between the metal and the molecule leads to charge transfer between them, and the molecular levels adjust due to Coulomb charging until the heterostructure is in equilibrium. Under bias the contact chemical potentials split by the applied voltage ($`\mu _2\mu _1=eV`$). As long as both potentials lie in the HLG, all HOMO levels are occupied and LUMO levels unoccupied, and there is essentially zero current. Once the bias is large enough that a contact chemical potential crosses a molecular level, that level is filled by one contact and emptied by the other, and starts conducting current. Thus the specific levels contributing to conduction for either bias direction depend on the way $`\mu _1`$ and $`\mu _2`$ are disposed relative to the molecular levels under bias.

One can get an asymmetric I-V with a symmetric molecule provided the latter is coupled strongly enough to the substrate to be in equilibrium with it, resulting in $`\mu _1=E_F`$. The potential of the other contact (say, an STM tip) moves freely under bias, $`\mu _2=E_F+eV`$ (Fig. 2a). If furthermore there is a large density of metal-induced gap states (MIGS) in the gap, then the electrostatic potential and the molecular levels stay pinned to $`\mu _1`$ and don’t vary with $`V`$. For positive and negative substrate bias, $`\mu _2`$ crosses the LUMO and HOMO levels respectively, yielding a strongly asymmetric I-V, since the LUMO and HOMO transmissions are quite different in general. The conductance gap is then given by the HLG, a property intrinsic to the molecule itself.

In practice, however, spatially symmetric molecular species typically exhibit symmetric I-Vs, with a conductance gap that varies from experiment to experiment . The MIGS are usually not appreciable causing the electrostatic and chemical potentials to separate. The average electrostatic potential across the molecule is $`V/2`$, which shifts the levels along with the applied bias. Relative to the molecular levels therefore, the contact potentials move in opposite directions symmetrically, $`\mu _{1,2}=E_feV/2`$ (Fig. 2b). The same molecular level (HOMO in the figure) is crossed for either bias by the contact chemical potentials, leading to a symmetric I-V, with a conductance gap given by $`4(E_fE_{\mathrm{HOMO}})`$ . The gap is no longer the HLG, but depends on both the molecular chemistry and the contact microstructure.

The above non self-consistent description of molecular conduction can be put on a quantitative footing by using an appropriate molecular Fock matrix $`F`$ (ab-initio or semi-empirical), followed by a non-equilibrium Green’s function (NEGF) formulation of transport . For a given Fock matrix $`F`$, overlap matrix $`S`$, and contact self-energies $`\mathrm{\Sigma }_{1,2}`$ with corresponding broadenings $`\mathrm{\Gamma }_{1,2}=i\left(\mathrm{\Sigma }_{1,2}\mathrm{\Sigma }_{1,2}^{}\right)`$, the energy levels are given by the poles of the nonequilibrium Green’s function $`G`$, while their occupancies are obtained from the corresponding density matrix $`\rho `$ and the contact Fermi functions $`f_{1,2}`$:

$`G(E)`$ $`=`$ $`\left(ESF\mathrm{\Sigma }_1\mathrm{\Sigma }_2\right)^1`$ (1)
$`\rho `$ $`=`$ $`\left(1/2\pi \right){\displaystyle _{\mathrm{}}^{\mathrm{}}}𝑑E\left(f_1G\mathrm{\Gamma }_1G^{}+f_2G\mathrm{\Gamma }_2G^{}\right)`$ (2)
$`f_{1,2}(E)`$ $`=`$ $`\left[1+\mathrm{exp}((E\mu _{1,2})/k_BT)\right]^1.`$ (3)
The number of electrons $`N`$ and the steady-state current $`I`$ are then given by:

$`N`$ $`=`$ $`2(\mathrm{for}\mathrm{spin})\times \mathrm{trace}(\rho \mathrm{S})`$ (4)
$`I`$ $`=`$ $`{\displaystyle \frac{2e}{h}}{\displaystyle _{\mathrm{}}^{\mathrm{}}}𝑑E\mathrm{trace}(\mathrm{\Gamma }_1G\mathrm{\Gamma }_2G^{})\left[f_1(E)f_2(E)\right].`$ (5)
The important point to notice is that since the same molecular level is being crossed both ways, the current is symmetric in the coupling constants $`\mathrm{\Gamma }_{1,2}`$ and one is stuck with a symmetric I-V for a symmetric molecule, no matter how asymmetric the contacts are.

The asymmetric I-V cannot simply be explained by suggesting that the average electrostatic potential across the molecule is $`\eta V`$ , $`\eta `$ decreasing from 0.5 as a contact is drawn out. Such a theory yields an asymmetry only in the onset voltages for conduction, rather than a dragged out I-V as in Fig. 1 (the latter actually corresponds to different conductance peak values in the two bias directions). One will then need to invoke a voltage-dependent $`\eta `$ to explain Fig.1, which formally amounts to our self-consistent charging description below.

Self-consistent description (Charging induced asymmetry) The above description of molecular conduction does not include the effects of charging and electronic Stark shift back on the levels. For a small molecule with a large ($`1`$ eV) capacitative charging energy, charging effects need to be taken into account self-consistently. In the following, we show that such effects can lead to contact-induced asymmetries of the sort observed in Fig. 1.

The effect of differential charging on the I-V asymmetry is explained schematically in Fig. 3 for a single level. Let us suppose that the contacts are strongly asymmetric ($`\mathrm{\Gamma }_1\mathrm{\Gamma }_2`$). For negative bias on the strong contact (a), the latter is trying to fill the nearest (HOMO) level, while the weaker contact is trying to empty it, with the net result that the HOMO level stays filled, with current onset set by the voltage where $`\mu _2`$ first crosses the (neutral) molecular level. For positive bias (b), however, the HOMO level is emptied out, which charges up the molecule positively. This adds a self-consistent charging energy that lowers all the energy levels, postponing thereby the point where the HOMO is crossed by $`\mu _1`$. In effect, this stretches out the voltage axis, leading thus to a smaller conductance for positive bias on the stronger contact, as mentioned earlier. For LUMO-based conduction the argument is reversed, since filling the LUMO level charges up the molecule negatively.

We illustrate self-consistent charging effects in a PDT molecule modeled by a extended Hückel  description of the Fock matrix $`F`$, coupled to the NEGF equations described earlier. The self-energies are calculated for Au(111) contacts using a recursive technique . Charging effects are incorporated in $`F`$ by adding a term $`U_{\mathrm{SC}}`$ describing the deviation from the equilibrium electron count $`N_0`$ within the local density approximation

$$U_{\mathrm{SC}}=U_0\left(NN_0\right),$$
(6)
and solving for $`F`$ self-consistently with equations 3 and 5. The constant charging energy $`U_0`$ ($`0.7`$eV per electron) corresponds to a flat electrostatic potential profile in the molecule , and serves to shift all the energy levels rigidly by a constant.

Fig. 4 shows the I-V characteristic for PDT with weak symmetric contacts (central graph), with contact self-energies 0.1 times their chemisorbed values, assuming HOMO conduction ($`E_f=10`$ eV). Weakening the coupling with the right contact ($`\mathrm{\Gamma }_2=0.2\mathrm{\Gamma }_1`$) stretches the voltage axis along contact 1 (lower figure). The I-V asymmetry can be switched (upper figure) either by switching the contact couplings, or by raising $`E_f`$ enough to generate LUMO-based conduction.

The calculated trend in the I-V characteristics agrees qualitatively with the experiments on symmetric molecules with asymmetric contacts . In break-junction experiments in general, the molecules are likely to adsorb separately onto the two contacts symmetrically , leading to symmetric I-Vs  even for asymmetric contacts. In carefully controlled break-junction experiments, however, a single molecule is expected to couple simultaneously with both contacts. This allows one to induce asymmetry easily by manipulating the contacts, changing the I-V from symmetric to asymmetric and back , as well as flipping the sense of the asymmetry by interchanging contact couplings. Weak I-V asymmetries are also seen in STM measurements of symmetric molecules such as PDT , where the conductance is lower for positive substrate bias. Since the coupling of the molecule with the STM contact is evidently weaker than with the substrate, the above asymmetry implies that conduction in PDT is HOMO-based.

In summary, we have established that even for spatially symmetric molecules, contact asymmetry can induce an asymmetric I-V through differential charging, the sense of the asymmetry depending on whether conduction is through a HOMO or a LUMO level.

We would like to thank M. Paulsson, R. Reifenberger, D. Janes and H. B. Weber for useful discussions. This work has been supported by NSF and the US Army Research Office (ARO) under grants number 9809520-ECS and DAAD19-99-1-0198.


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# Thermoluminescence of Simulated Interstellar Matter after Gamma-ray Irradiation

## 1 Introduction

Interstellar matter will be irradiated by electromagnetic energy and several cosmic ray particles, such as gamma rays, neutrons, protons and heavy-ions etc. Irradiation will cause some changes in these materials, especially to their optical properties. Investigation of this problem is expected to advance our understanding of interstellar and circumstellar matter. Especially, it is well known that extremely large fluxes of neutrons and gamma-rays have been emitted during super-nova explosions and during the so called Hayashi-phase in the early stage of protostellar systems. Moreover, interplanetary-dust is often irradiated by gamma rays and fast neutrons during the periods of flare activity on the sun, which is always repeated. Interstellar and circumstellar space is typically at extremely low temperature and is always irradiated over cosmological time-scale.

Though little is known about irradiation environment outside of our solar system, it is natural to suppose that there are the regions with sufficient strength of irradiation to cause thermoluminescences, for example, a region of not so extremely far from a super nova explosion or not so far from a source of gamma ray emission, and/or long time irradiation at extremely low temperature. The effect of this radiation will accumulate in the low temperature environment. It will be observed provided that the condition to release the accumulated energy is realized in circumstellar space.

The effects of irradiation on simple single crystals such as $`\mathrm{SiO}_2,\mathrm{CaCO}_3`$ and $`\mathrm{CaF}_2`$ have been investigated by several authors (Nakagawa et al. nakagawa1 (1988), Nakagawa et al. nakagawa2 (1999)) from the viewpoint of solid state physics or material science. However, irradiation of materials of interstellar matter has not been studied. It may then be worthwhile to investigate the effects of irradiation on simulated interstellar matter such as forsterite, enstatite and carbonates. Forsterite and enstatite have been found by many ISO observations in both young and evolved stars and in our own solar system (Waters et al.waters (1998), Malfait et al. malfait (1998), Wooden et al.wooden (1999)). Carbonates such as dolomite ($`\mathrm{CaMg}(\mathrm{CO}_3)_2`$), breunnerite ($`\mathrm{Mg}(\mathrm{Fe},\mathrm{Mn})(\mathrm{CO}_3)_2`$), calcite ($`\mathrm{CaCO}_3`$), and $`\mathrm{Mg}`$, $`\mathrm{Ca}`$-bearing siderite ($`\mathrm{FeCO}_3`$) were found in CI chondrite (Endress, Zinner and Bischoff endress (1996)). Especially, it should be noted that the broad emission feature responsible for extended red emission(ERE) appears at about the 500 – 900 nm region in many reflection nebulaes, and the Red Rectangle nebula shows sharp emission features over a broad band (Witt and Boroson witt (1990)). In the Red Rectangle nebulae, both PAH-features and crystalline silicates (forsterite and enstatite) were observed (Waters et al., 1998). The effect of irradiation on the optical properties of the simulated interstellar materials such as forsterite and enstatite by gamma rays and neutrons at low temperature are very interesting.

## 2 Features of Thermoluminescence spectrum

Bulk samples such as forsterite, $`\mathrm{Mg}_2\mathrm{SiO}_4`$, natural olivine from Egypt, orthoenstatite $`\mathrm{MgSiO}_3`$ and natural magnesite $`\mathrm{MgCO}_3`$ from the Democratic People’s Rep. of Korea were irradiated with gamma-rays to a dose of about $`10.4\times 10^4`$ Gy $`(\mathrm{J}/\mathrm{Kg})`$ in liquid nitrogen using the $`{}_{}{}^{60}\mathrm{Co}`$ gamma-ray irradiation facility of Kyoto University Reactor. The gamma-rays of $`{}_{}{}^{60}\mathrm{Co}`$ have two peaks at 1.1 MeV and 1.3 MeV. Our samples of forsterite and enstatite were synthesized by Takei and Kobayashi (1974), and Tachibana (2000) using the CZ (Czochralski) and Flux method, respectively with high accuracy. The bulk of the irradiated forsterite is triangular-shaped (about $`6\times 8\times 15`$ mm size, about 1 mm thickness) and weights about 138 mg. The irradiated enstatite consists of several small fragments (about 1 - 2 mm size) and the total weight is about 114 mg.

We have measured the thermoluminescence spectra of these samples using a spectrophotometer (including a CCD camera, Princeton Instruments, Inc.). The sample is put on the thermally-isolated plate, which has previously been cooled to liquid nitrogen temperature. The luminescence emission during warming is introduced to the CCD measuring system using an optically transparent fiber. The color of forsterite changed to dark-white and -gray (rather dark red-violet) after gamma-ray irradiation. The time of warming the samples from liquid nitrogen temperature to room temperature (333 K) is about 15 min. It should be noted that this time length is sufficient to observe the thermoluminescence, that is, photon is emitted at the thermal equilibrium state.

Fig.1 shows the luminescence spectra of forsterite $`(\mathrm{Mg}_2\mathrm{SiO}_4)`$ after Gamma-ray irradiation. It shows a rather intense broad peak at about 645–655 nm (and a weak broad peak at 400–440 nm), and a sharp peak at 610 nm. The sharp peak at 610 nm appears as the sample warms from 200K to room temperature. Other weak peaks at 590, 595, and 705 nm appear distinctly at above 200 K. The broad peak at 645-655 nm becomes suddenly strongest at 272 – 307 K , and the weak peaks fade into background. Above 307 K, the luminescence becomes weak gradually and another peaks at 595, 605, 705, 710 nm become prominent. The previous preliminary data of another sample of irradiated forsterite, its weight about 244 mg, have shown almost the same luminescence spectra, but it seems that the earliest luminescence starts at somewhat low temperature. Fig.2 shows the total strength of luminescence in Fig.1. A magnification of the emitted thermoluminescences spectrum of the most low-temperature at the range about 164-200K in Fig.1 is shown in Fig.3.

In contrast, the luminescence is scarcely visible in natural olivine (from Egypt, $`\mathrm{Fo}_{90}`$). As for enstatite, we have detect the luminescence spectra, which is shown in Fig.4. Two broad peaks appear at about 545 and 760 nm, and these peaks are very weak compared with the spectra of forsterite. The weight of enstatite used was 114 mg, while that of forsterite was 138 mg as mentioned before.

Fig.6 shows the measurement of luminescence spectra of magnesite $`\mathrm{MgCO}_3`$ after Gamma-ray irradiation. The spectrum of $`\mathrm{MgCO}_3`$ shows a very broad peak at about 660nm, and this peak becomes strong at 350 – 375 K. The irradiated magnesite is a bulk sample (about $`5\times 5\times 2`$ mm size) and its weight is 93 mg. It should be emphasized that the thermoluminescence of $`\mathrm{MgCO}_3`$ also has sufficient strength to be visible easily. The color of magnesite changed to a rather white-gray with pink-yellow tendency after gamma-ray irradiation.

We have also measured the thermo-dependence of luminescence of calcite. The present luminescence of calcite is shown in Fig.7 and Fig.8. The intensity becomes stronger as temperature increased from 77 K, and the peak position is 620-640 nm at 300 K. Above 300 K, the intensity became further stronger, and at 327 - 337 K the intensity became strongest, the shape of luminescence changed and the peak position shifts to around 605 nm. Higher temperature than 337 K, the intensity became weak.

## 3 Related problems and the other measurements

We also investigated the effect of irradiation on both a bulk sample and particle samples embedded in polyethylene using neutrons to a dose of $`8\times 10^{16}n_f/\mathrm{cm}^2`$ at 10 K and 70 K using the low-temperature irradiation facility of Kyoto University Reactor (KUR-LTL: Low Temperature Loop)(Okada et al., 2001). After neutron irradiations of 75 hour, samples are stored in liquid nitrogen for several months to wait a decay of radioactivity.

We measured the absorption coefficient of a neutron-irradiated forsterite and enstatite particles using a FTIR spectrometer(Nicolet, Nexus 670) over the wavelength range from 30 – 100 $`\mu m`$. The samples were irradiated at 70 K using a neutrons in September, 2000. The gross feature of spectrum show no apparent difference from the spectrum (Koike C. et al. koikeC1 (2000), koikeC2 (2000)) taken before irradiation. One of the reasons for this result may be that the fast neutrons strongly collide with hydrogen atoms in the polyethylene and only weakly collide with sample particles dispersed in polyethylene.

We have also measured the thermoluminescence spectrum of neutron-irradiated bulk sample of forsterite, which is shown in Fig. 5. At low-temperature, two peaks appeared at about 450 and 650 nm, but above 253K one peak at 450nm became weak. The peak at 650nm is almost the same as Gamma-ray irradiated case, however, the strength of luminescence is considerably weak. This reason is not known yet.

For future irradiation experiments using a stronger beam of neutrons in the center of the reactor, we are interested in an accurate measurement of the impurity component in our forsterite sample, because impurity component with long a half period brings serious difficulties in measurements of irradiated samples. Previously, Takei and Kobayashi ( takei (1974)) reported that the spectrographic analysis shows that the forsterite sample is pure, but using neutron activation analysis, an infinitesimal quantity of Ir at about 16–18 wt ppm had been found. This level of Ir impurity is below the detection limit of the spectrographic analysis. We have also measured our sample using radio activation analysis, and confirmed that our sample is almost pure; that is, other elements except for $`\mathrm{Mg},\mathrm{Si},\mathrm{O}`$ and an infinitesimal quantity of Ir are not detected.

## 4 Similarity to ERE of Red Rectangle Spectrum

It is remarkable fact that the observed spectrum of ERE (Extended Red Emission) of the Red Rectangle (Witt and Boroson witt (1990)) given in Fig. 9 shows characteristic feature. As for carriers of ERE, possible size effect of crystalline silicon nanoparticles has been discussed (Ledoux G. et al. Ledoux (2001)). It has been shown that the photoluminescence spectra of these nanoparticles can explain the gross structure of ERE spectra, such as the peak position and the full width at half maximum of ERE spectra etc. However, evidence of existence of crystalline silicon has not yet been observed. (Li and Draine Li1 (2001),Li2 (2001))

We have interested that the luminescence of forsterite is very similar to ERE of Red Rectangle (peak at 652-684 nm, half width 70-90 nm) among many objects. Generally, ERE from interstellar dust consists of a broad, featureless emission band peaking at 610-820 nm, and width 60-100 nm. Among many objects, Red Rectangle show strong emission of one order stronger and exhibits the characteristic feature. Furthermore, crystalline silicates such as forsterite and PAH dust had been founded in Red Rectangle by ISO observations. The present irradiated forsterite also shows very strong luminescence (peak at 640-660 nm) at about 280-308 K and half width of about 100 nm, and characteristic peaks at 590, 595, and 705nm.

It should be also remembered that forsterite and enstatite have been found by many ISO observations in many oxygen rich young and evolved stars. However, ERE is observed in many carbon rich stars. It is important to note that Red Rectangle is very interesting object with both carbon and oxygen rich characteristics, that is, both forsterite and PAH were found. It should be emphasized that our thermoluminescence spectrum of forsterite at about 645–655 nm and at 590 nm is very similar to the ERE of the Red Rectangle.

## 5 Discussion

For the irradiation circumstance, little is known around ERE object. However, it should be noted that interstellar and circumstellar space is typically at extremely low temperature and is always irradiated by electromagnetic radiation and by cosmic ray particles over cosmological time-scale. Furthermore, it is well known that extremely large fluxes of neutrons and gamma-rays have been emitted during super-nova explosions. The effect of this radiation will accumulate in the low temperature environment. It will only be observed provided that the condition to release the accumulated energy is realized in circumstellar space. This may be occur when irradiated dust move to a warmer domain in interstellar or circumstellar environment.

The accumulated energy in irradiated matter is released by thermoluminescence when the matter is warmed. The rate of this release is dominated by Boltzman factor, and in extremely low temperature its rate is practically infinite. In connection with this problem, it is interesting fact that the thermoluminescence spectrum of particles in Tyrrhenian Sea exhibits the typical peak at the layer of year 1054, 1006, 1181 etc., corresponding to the year of super-nova explosions (Castagnoli G. C. et al., Castagnoli (1982)). In their estimate, the energy emitted during super-nova explosions of Crab nebula at year 1054 is about $`10^{47}\mathrm{J}`$ and the estimated flux of energy at the point of distance of the radius of the Galaxy is about $`10^5\mathrm{J}/\mathrm{m}^2`$.

Though most energies of explosions are carried by neutrinos, a certain rate will be carried by X and gamma rays. It will be possible in extremely low-temperature environment such as interstellar or circumstellar space, the effects of irradiation are ”frozen” and almost stable in extremely long time, and various irradiation effects, such as often observed super-nova explosions or always irradiated cosmic rays, are accumulated.

The irradiation on matter generally cause lattice defects of crystal, and a certain kind of this effect is observed in thermoluminescence. It is known in many experiences that the irradiation effect on solid can be erased by annealing it to several hundred degrees. In other word, the effects of irradiation remains in a certain kind of form below this temperature and it may be observed still in effects different from the thermoluminescence.

## 6 Summary

In this paper, we report the data for gamma-ray irradiation of some simulated interstellar materials. Forsterite $`(\mathrm{Mg}_2\mathrm{SiO}_4)`$, enstatite $`(\mathrm{MgSiO}_3)`$ and magnesite $`(\mathrm{MgCO}_3)`$ exhibit interesting thermoluminescences spectra.

We have emphasized that the thermoluminescence of forsterite appears at low temperature at about 160-200K. In particular, it should be emphasized that the spectrum of forsterite at about 645–655 nm and at 590 nm is very similar to the ERE of the Red Rectangle. (Witt and Boroson witt (1990)) It should be noted that possible size effect of crystalline silicon nanoparticles can explain the gross structure of ERE spectra (Ledoux G. et al. Ledoux (2001)). However, this model can explain only the gross structure of spectrum of ERE, and seems not to explain the characteristic features of 590nm. The most interesting fact of size effect is the peaks of gross structure of luminescence shifts depending on the size of nanoparticles. It is interesting problem to examine possible existence of similar effect in forsterite nanoparticles.

Finally, the irradiation on matter is expected to cause various effects on matter in addition to thermoluminescence effects. Investigating these effects in the context of astrophysics is further problem.

###### Acknowledgements.

The authors would like to express their sincere thanks to Prof. Tsuchiyama A., who provided superior samples of simulated interstellar matter such as forsterite and enstatite. We would like also to acknowledge members of Prof. Atobe’s group of Naruto University of Education for using their equipment including the sample holder with thermo controller. This work was supported by the KUR projects (12062, 13p1-6). Part of this work was supported by Grant-in-Aid of Japanese Ministry of Education, Science, and Culture (12440054).