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Holographic Gratings and Data Storage in Azobenzene-Containing Block Copolymers and Molecular Glasses

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Complex Macromolecular Systems II

Part of the book series: Advances in Polymer Science ((POLYMER,volume 228))

Abstract

This review covers synthesis, materials development, and photophysics of azobenzene-containing block copolymers as potential media for reversible volume holographic data storage. For high-density holographic data storage, volume gratings must be inscribed in millimeter-thick samples to achieve efficient angle multiplexing. It is demonstrated that block copolymers with azobenzene side-groups in the minority block develop no detrimental surface relief structures and exhibit superior performance regarding volume gratings, compared to homopolymers and statistical copolymers. Several material concepts for optimizing the refractive index modulation and the stability of volume gratings are presented. Stabilities of more than 2 years were achieved. Most important is the development of polymer blends comprising the azobenzene-containing block copolymer and an optically transparent homopolymer. This enables the preparation of millimeter-thick samples with the required optical density of ∼ 0. 7 at the writing wavelength by conventional injection molding techniques. The inscription of up to 200 holograms at the same lateral position was demonstrated. In addition, more than 1,000 write/erase cycles can be performed. This is the first time that the inscription and erasure of the long-term stable angle-multiplexed volume gratings in a rewritable polymeric medium have been achieved by purely optical means. A second important application for azobenzene-containing materials is the controlled preparation of surface relief structures. It is demonstrated that azobenzene-containing molecular glasses are an ideal class for efficient formation of surface relief gratings (SRGs) with amplitude heights of more than 600 nm. Clear relationships can be established between the chemical structure of the molecules and the behavior of SRG formation. All results are in agreement with the gradient force model by Kumar et al. The surface patterns are stable enough to be transferred to a polymer surface via replica molding.

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Abbreviations

45∘ :

Electric field vector at an angle of 45∘ to the plane of incidence

AFM:

Atomic force microscopy

AIBN:

Azobisisobutyronitrile

ATRP:

Atom transfer radical polymerization

BS:

Beam splitter

c :

Cylindrical

CCD:

Charge-coupled device

CD:

Compact disc

d 0 :

1 Thickness of the film

Δd max :

Maximum SRG height

DSC:

Differential scanning calorimetry

\(\vec{E}\) :

Electric field vector of the incident light

f :

Gradient force

GPC:

Gel permeation chromatography

h :

Planck constant

HEMA:

Hydroxyethylmethacrylate

HOE:

Holographic optical element

I :

Intensity

J1 :

First order Bessel function

k :

Absorption coefficient

k b :

Boltzmann constant

λ:

Wavelength of laser beam

lcp:

Left circularly polarized light

m :

Miscible

M n :

Number average molecular weight

M w :

Weight average molecular weight

η:

Diffraction efficiency

n :

Refractive index of the sample

n 1 :

Refractive index modulation

n 1, max :

Maximum refractive index modulation

Δn :

Amplitude of the refractive index change between sample and air

NEXAFS:

Near-edge X-ray absorption fine structure

NMP:

Nitroxide mediated polymerization

NMR:

Nuclear magnetic resonance

ν:

Frequency

OD:

Optical density

p:

Electric field vector parallel to the plane of incidence

P:

Polarizer

P :

Polarization induced by the electric light field

PAP:

Photoaddressable polymers

PB:

Polybutadiene

PDI:

Polydispersity index

PDMS:

Poly(dimethyl)siloxane

PMMA:

Polymethylmethacrylate

POLMIC:

Polarized light microscopy

PS:

Polystyrene

rcp:

Right circularly polarized light

ROM:

Read-only memory

ru:

Repeating unit

s :

Sphere

s:

Electric field vector perpendicular to the plane of incidence

S′ :

Sensitivity

SAXS:

Small angle X-ray scattering

SRG:

Surface relief grating

τ1 :

Time constant of the build-up of the volume grating

τ2 :

Time constant of the build-up of the surface relief grating

t :

Writing time

T :

Temperature

T g :

Glass transition temperature

TEM:

Transmission electron microscopy

TGA:

Thermogravimetric analysis

THF:

Tetrahydrofuran

UV/vis:

Ultraviolet/visible

wA :

Normalized weight of block A

WAXS:

Wide-angle X-ray scattering

WORM:

Write-once read-many

θ:

Angle of incidence of the laser beam

Δφ:

Phase difference between volume and surface relief grating

χ:

Electrical susceptibility

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Acknowledgements

The authors are deeply indebted to Dr. Thomas Breiner, Dr. Carsten Frenz, Dr. Michael Häckel, and Dr. Ulrich Theissen for their contributions and their dedicated work during their Ph.D. theses at the University of Bayreuth. Daniela Kropp and Christina Löffler (Makromolekulare Chemie I) are gratefully acknowledged for their invaluable contributions in material synthesis and sample preparation.

HWS wishes to express his special gratitude to Helmut Ringsdorf for inspiring him in 1982 to synthesize and study the first azobenzene side chain liquid-crystalline polymers in his diploma thesis. As this chapter clearly demonstrates, the topic has now broad application potentials and is still fascinating to us.

The authors are grateful to the German Science Foundation for generously providing financial support for this work within the framework of the collaborative research centre SFB 481, project B2.

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Authors and Affiliations

  1. Institute of Physics, Bayreuther Institut für Makromolekülforschung (BIMF) University of Bayreuth, 95440, Bayreuth, Germany

    Hubert Audorff, Dietrich Haarer & Lothar Kador

  2. Macromolecular Chemistry I, Bayreuther Institut für Makromolekülforschung (BIMF) University of Bayreuth, 95440, Bayreuth, Germany

    Klaus Kreger, Roland Walker & Hans-Werner Schmidt

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  1. Hubert Audorff
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  2. Klaus Kreger
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  3. Roland Walker
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  4. Dietrich Haarer
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  5. Lothar Kador
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  6. Hans-Werner Schmidt
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Corresponding authors

Correspondence to Lothar Kador or Hans-Werner Schmidt .

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Editors and Affiliations

  1. Inst. Makromolekülforschung, LS für Makromolekulare Chemie II, Universität Bayreuth, Universitätsstr. 30, Bayreuth, 95440, Germany

    Axel H. E. Müller

  2. Inst. Makromolekulare Chemie I, Univ. Bayreuth, Bayreuth, 95440, Germany

    Hans-Werner Schmidt

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Dedicated to Prof. Dr. Helmut Ringsdorf on the occasion of his 80th birthday

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Audorff, H., Kreger, K., Walker, R., Haarer, D., Kador, L., Schmidt, HW. (2009). Holographic Gratings and Data Storage in Azobenzene-Containing Block Copolymers and Molecular Glasses. In: Müller, A., Schmidt, HW. (eds) Complex Macromolecular Systems II. Advances in Polymer Science, vol 228. Springer, Berlin, Heidelberg. https://doi.org/10.1007/12_2009_35

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