L. D. Sun

Online measurement of the optical anisotropy during the growth of crystalline organic films

We report a reflectance difference spectroscopy (RDS) investigation of the growth of para-sexiphenyl (p-6P) on a TiO2(110) single crystal substrate at 100, 300, and 400K. The results demonstrate that RDS is a powerful technique to monitor organic thin film growth from the submonolayer regime to device relevant thicknesses. Based on the polarization dependence of the optical absorption at characteristic wavelengths, the orientation and the crystalline properties of the organic molecules can be directly determined from the RD spectrum with an extremely high sensitivity.

A rotating-compensator based reflectance difference spectrometer for fast spectroscopic measurements

We present a new type of reflectance difference (RD) spectrometer for fast spectroscopic measurements based on a rotating-compensator (RC) design. The instrument uses a 1024 element Si photodiode linear array for simultaneous multiwavelength detection. High quality RD spectra covering a spectral range from 1.5 to 4.5 eV can be acquired within a few seconds. A detailed description of the working principle, the instrumentation, and the algorithms used for data collection and reduction is presented, followed by a discussion of errors introduced by lamp instability and optical imperfections of the compensator. Finally, to demonstrate the performance of the new RCRD spectrometer, we illustrate its application for the in situ, real-time monitoring of the initial stages of organic thin film growth of para-sexiphenyl (p-6P) on the Cu(110)-(2 x 1)O surface.

Layer inversion in organic heterostructures

Thermally activated layer inversion of ultrathin pentacene/para-sexiphenyl organic heterostructures is observed using a combination of reflectance difference spectroscopy and scanning tunneling microscopy. The heterostructures are formed by deposition of sub-monolayer pentacene (PEN) on top of well ordered para-sexiphenyl (p-6P) layers on Cu(110) at 15 K. When the sample temperature is raised, these heterostructures invert, with pentacene molecules diffusing through the para-sexiphenyl buffer layer and getting in direct contact with the substrate. The observed irreversible inversion demonstrates that the p-6P/PEN/Cu(110) is energetically preferred over PEN/p-6P/Cu(110). Furthermore, the onset temperature of the inversion increases with the layer thickness of para-sexiphenyl indicating a corresponding increase of the kinetic barrier for the inversion. Our results demonstrate the strong influence of the configuration of organic heterostructures on their thermal stability, especially for the very thin layers.

Optical referencing in differential reflectance spectroscopy

We report a new optical set-up for difference reflectance spectroscopy (DRS) measurements based on a two-beam configuration. By normalizing the reflected intensity from the sample surface with a reference signal that is directly proportional to the incident beam intensity, the calculated DR spectra become insensitive to the instability of the light source. As a result, a significantly improved signal-to-noise ratio is obtained and DR signals in the low 10−4 range can be measured reliably. This enables an extremely high sensitivity for surface studies using optical spectroscopy.

Layer resolved evolution of the optical properties of α-sexithiophene thin films.

We report a combined reflectance difference spectroscopy and scanning tunneling microscopy study of ultrathin α-sexithiophene (6T) films deposited on the Cu(110)-(2×1)O surface. The correlation between the layer resolved crystalline structure and the corresponding optical spectra data reveals a highly sensitive dependence of the excitonic optical properties on the layer thickness and crystalline structure of the 6T film.

Revealing the buried interface: para-sexiphenyl thin films grown on TiO2(110).

The thickness dependent optical and electronic structure of para-sexiphenyl thin films grown on TiO(2)(110) at around 400 K reveals that the substrate is first wet by one monolayer of molecules lying with their long axis parallel to the [001] direction of the substrate, while the molecules in subsequent layers are almost standing upright. Whilst ultraviolet photoemission spectroscopy (UPS) is sensitive to the molecules in the outermost layer, reflection difference spectroscopy (RDS) shows that the molecules at the buried interface do not dewet and maintain the orientation of the original wetting monolayer.

Optical and mechanical anisotropies of oriented poly(ethylene terephthalate) films

Reflectance difference spectroscopy (RDS) is used to characterize the optical anisotropy of thin, biaxially oriented poly(ethylene terephthalate) films. Molecular orientation in these films results in birefringence and thus gives rise to a RDS signal, which changes characteristically with external strain. A clear link between the optical and mechanical anisotropies can be established by comparing the azimuthal dependence of the elastic modulus with the RDS signal. Online measurements during tensile tests provide information on the evolution of the optical properties as a function of external strain, thus making RDS a highly sensitive probe for strain in oriented polymers.

Optical characterization of thin nickel films on polymer substrates using reflectance difference spectroscopy

We have used reflectance difference spectroscopy (RDS) and its extension, azimuth-dependent RDS (ADRDS), to study the properties of sputtered and evaporated nickel films on biaxially oriented poly(ethylene terephtalate) (PET) films in a roll to roll web-coating process. From the full set of ADRDS spectra we extract and analyze both the intrinsic RDS spectra and the azimuthal orientation of the effective optical anisotropy of the samples. From the latter, contributions to the RDS spectra arising from the nickel layer and the PET substrate with different orientations of the optical eigenaxes can be inferred. We find an attenuation of the characteristic RDS signal of the PET substrate with increasing nickel film thickness which is in good agreement with the theoretical prediction. For film thicknesses above 20 nm another contribution to the RDS signal attributed to the optical anisotropy of the deposited nickel layers can be observed. Its strength depends on the deposition method, and is considerably larger ...

Retardation correction for photoelastic modulator-based multichannel reflectance difference spectroscopy

The wavelength dependence of the retardation induced by a photoelastic modulator (PEM) is a central issue in multichannel modulator-based spectroscopic ellipsometry and reflectance difference spectroscopy (RDS), where the optical signal is detected simultaneously at different wavelengths. Here we present a refined analysis of the modulator crystals retardation and its effect on the signal quality. Two retardation correction schemes that take into account the actual wavelength dependence of the stress-optic coefficient are introduced. It is demonstrated experimentally that both methods provide a better correction than the procedure currently used in multichannel RDS. We define quality factors to evaluate the actual performance of the multichannel detection system as compared with a wavelength adaptive single-channel experiment. These quality factors thus provide a useful guideline for choosing the appropriate PEM retardation or reference wavelength in a multichannel experiment.

Normal-incidence reflectance difference spectroscopy based on a liquid crystal variable retarder

We propose liquid crystal variable retarder-based reflectance difference spectroscopy for normal-incidence measurements. Principles, instrumentation, data collection and reduction, and calibration procedures are provided. The signal noise is better than 10-3, and the spectral range is from 1.6 to 2.4 eV with 346 photon energy channels. As a demonstration, reflectance difference signals of a multilayer pentacene film on poly (ethylene terephthalate) (PET) film are presented with different polarization azimuths. The characteristic peaks at 1.8 and 1.97 eV, corresponding to the Davydov splitting of pentacene crystal, are observed, which indicate well-ordered in-plane anisotropic structure of pentacene crystal film on PET. Thanks to normal incidence, this design is immune to adjusting the optical structure for the measurements with different working distances, and the objective lens is easily integrated to realize microarea measurements.