Copper Phthalocyanine (CuPc) Thin Films and Nanostructures - Growth and Device Applications
Author(s)
Din, Salahud
Type
Thesis or dissertation
Abstract
The development and utilisation of phthalocyanine (Pc) materials for practical applications has
been subject of intense research due to their desirable optical, electrical, and recently discovered magnetic
properties. Typically, in crystalline organic materials the charge transport, light absorption and
magnetisation are anisotropic and strongly depend on structure, morphology and molecular orientation.
Hence, an understanding of growth mechanism and controlled fabrication of thin films and
nanostructures is essential for tailoring properties desirable for specific applications. e.g., for OFETs,
crystalline thin films or one-dimensional nanostructures.
Recently, vast advancement has been made in developing functional organic films including sublimation
in (ultra) high vacuum using organic molecular beam deposition (OMBD). This environment
can provide the essential material purity and structural reproducibility required in future high performance
optoelectronic device applications, but is unfortunately costly. In this thesis, we introduce
a lesser-known technique, organic vapour phase deposition (OVPD), operating at lower cost but still
maintaining high purity. The morphology, crystallinity, spectroscopic characteristics and structure of
copper phthalocyanine (CuPc) thin films and nanostructures have been investigated and their dependence
on deposition conditions, i.e., substrate temperature and substrate type has been studied.
We compare films obtained by OMBD and OVPD and find different morphological and structural
changes; the surface morphology changes from granular to larger nano-fibrous and nano-whiskers
with increasing substrate temperatures. In OMBD, the structure in a small proportion of the film
changes from α-CuPc to β-CuPc at a substrate temperature of 200 oC. In the case of OVPD films,
extensive study of the influence of parameters such as deposition pressure, deposition time and source to
substrate distance is performed and variation in film morphology, texture, structural composition and
molecular orientation is observed. We find that by successive growth of films produced by OMBD and
OVPD, the molecular orientation can be controlled by the first “seed” layer. With further processing
and optimisation, it is hoped that this could be used to create interpenetrating networks of different
organic materials and optimal molecular orientation. We also demonstrate the fabrication using OVPD
of high density CuPc nanowires with typical diameters between 10 - 100 nm, high directionality, and
exceptional aspect ratios. We show that these nanowires are of a new crystal phase, named eta-CuPc.
Lastly, OFETs fabricated with OMBD and OVPD grown CuPc thin films and nanowires are
characterised. The current on/off ratio, mobilities and threshold voltage for thin films produced by
the two methods are comparable and similar to what has been reported in literature. In contrast,
OFETs with CuPc nanowires show remarkable improvement in turn-on voltage, while mobilities also seem to improve dramatically, although this is difficult to quantify. The challenges in growing CuPc
nanowires directly on FETs with precise control of position and directionality are reviewed. The key
issues that need to be resolved for future applications of these one-dimensional nanostructures are
identified and are subject of on-going research.
To conclude, this work has made important contribution in the efforts to develop, improve and
enhance the deposition methods for fabricating functional thin films and nanostructures of CuPc
material for use in organic electronic devices.
been subject of intense research due to their desirable optical, electrical, and recently discovered magnetic
properties. Typically, in crystalline organic materials the charge transport, light absorption and
magnetisation are anisotropic and strongly depend on structure, morphology and molecular orientation.
Hence, an understanding of growth mechanism and controlled fabrication of thin films and
nanostructures is essential for tailoring properties desirable for specific applications. e.g., for OFETs,
crystalline thin films or one-dimensional nanostructures.
Recently, vast advancement has been made in developing functional organic films including sublimation
in (ultra) high vacuum using organic molecular beam deposition (OMBD). This environment
can provide the essential material purity and structural reproducibility required in future high performance
optoelectronic device applications, but is unfortunately costly. In this thesis, we introduce
a lesser-known technique, organic vapour phase deposition (OVPD), operating at lower cost but still
maintaining high purity. The morphology, crystallinity, spectroscopic characteristics and structure of
copper phthalocyanine (CuPc) thin films and nanostructures have been investigated and their dependence
on deposition conditions, i.e., substrate temperature and substrate type has been studied.
We compare films obtained by OMBD and OVPD and find different morphological and structural
changes; the surface morphology changes from granular to larger nano-fibrous and nano-whiskers
with increasing substrate temperatures. In OMBD, the structure in a small proportion of the film
changes from α-CuPc to β-CuPc at a substrate temperature of 200 oC. In the case of OVPD films,
extensive study of the influence of parameters such as deposition pressure, deposition time and source to
substrate distance is performed and variation in film morphology, texture, structural composition and
molecular orientation is observed. We find that by successive growth of films produced by OMBD and
OVPD, the molecular orientation can be controlled by the first “seed” layer. With further processing
and optimisation, it is hoped that this could be used to create interpenetrating networks of different
organic materials and optimal molecular orientation. We also demonstrate the fabrication using OVPD
of high density CuPc nanowires with typical diameters between 10 - 100 nm, high directionality, and
exceptional aspect ratios. We show that these nanowires are of a new crystal phase, named eta-CuPc.
Lastly, OFETs fabricated with OMBD and OVPD grown CuPc thin films and nanowires are
characterised. The current on/off ratio, mobilities and threshold voltage for thin films produced by
the two methods are comparable and similar to what has been reported in literature. In contrast,
OFETs with CuPc nanowires show remarkable improvement in turn-on voltage, while mobilities also seem to improve dramatically, although this is difficult to quantify. The challenges in growing CuPc
nanowires directly on FETs with precise control of position and directionality are reviewed. The key
issues that need to be resolved for future applications of these one-dimensional nanostructures are
identified and are subject of on-going research.
To conclude, this work has made important contribution in the efforts to develop, improve and
enhance the deposition methods for fabricating functional thin films and nanostructures of CuPc
material for use in organic electronic devices.
Date Issued
2012
Date Awarded
2013-03
Advisor
Heutz, Sandrine
Sponsor
Engineering and Physical Sciences Research Council
Publisher Department
Materials
Publisher Institution
Imperial College London
Qualification Level
Doctoral
Qualification Name
Doctor of Philosophy (PhD)