Chapter One Page 5: spelling error Reply: change ‘stared’ To ‘started’ Page 5: spelling error Reply: change ‘summaries’ To ‘summarizes’ Page 5: grammar error Reply: delete ‘beforehan
Trang 1Summary of Amendments
Cover Page
The examiner suggests changing the thesis title
Reply: not changed
Explanation: This thesis describes the basic synthesis of new materials with the required semiconducting properties for further possible applications in molecular electronics In addition, we have investigated the electrical properties of individual and stacked nano-plates which showed interesting behavior We stopped short of device evaluation because of lack of time We feel that the title is appropriate
Trang 2Chapter One
Page 5: spelling error
Reply: change ‘stared’
To ‘started’
Page 5: spelling error
Reply: change ‘summaries’
To ‘summarizes’
Page 5: grammar error
Reply: delete ‘beforehand’ in ‘However, beforehand fabrication of
nanomaterials…’
Page 6: expression modification
Reply: change ‘strong and weak aspects’
To ‘strength and weakness’
Page 6: grammar error
Reply: change ‘photoresist’
To ‘photoresists’
Page 7: expression modification
Trang 3Reply: change ‘lay-by-lay’
To ‘layer-to-layer’
Page 7: definitions
Reply: add ‘Scanning Tunneling Microscope’ and ‘Atomic Force
Microscopy’ as the full names of STM and AFM, respectively
Page 7: grammar error
Reply: delete ‘of’ in ‘fabricate of nanostructured patterns’
Page 7: Add more details of reference 16 and 17
Reply: add in ‘The most remarkable demonstrations are the placing
of atoms in a particular location (reference 16) and the construction
of a quantum corral of 48 Fe atoms by STM (reference 17)’
Page 7: the definition
Reply: add ‘Molecular Beam Epitaxy’ as the full name of MBE
Page 9: expression modification
Reply: change ‘fill in pores’
To ‘fill into the pores’
Trang 4Page 10: expression modification
Reply: change ‘derivative’
To ‘derivatives’
Page 11: expression modification
Reply: change ‘variations reaction’
To ‘variations of reaction’
Page 11: expression modification
Reply: change ‘no further purification process is needed’
To ‘no further purification is needed’
Page 12: grammar error
Reply: change ‘the nanofiber’
To ‘the nanofibers’
Page 12: expression modification
Reply: change ‘is companied by’
To ‘is accompanied by’
Page 12: grammar error
Reply: change ‘results in granular particulates’
Trang 5To ‘results to granular particulates’
Page 12: The examiner questions the word ‘predisposition’
Reply: not changed
Explanation: the word ‘predisposition’ (Adv Mater 2009, 21, 1487)
means the tendency for conjugated polymers to form linear anisotropic structures
Page 14: expression modification
Reply: change ‘A plethora of analytes are reported to be detected,130-142
which are classified into one or more of the five established mechanisms.130 ‘
To ‘A plethora of analytes have already been reported 130-142
The
mechanisms are classified into the five established models 130 ’
Trang 6Chapter Two Page 27: the definition
Reply: add in Nomenclature ‘(An)’ as the short name for aniline
Page 30: The examiner questions how the diffraction rings and spots (Fig 2.1c) are corresponding to the amorphous PANI spheres and gold nanoparticles, respectively
Explanation: Polymer chains have regular arrangements in local scale, which corresponds to the weak rings; while the bright spots are due to specific gold crystal structures
Page 31: The examiner questions how the broad peak centered at
2θ = 29 o is ascribed to PANI
Explanation: The very weak and wide peak centered at 2θ = 29 o is associated with X-ray diffraction of amorphous regions in PANI It is reported that protonated PANI powders generally have the ES-I structure, which show a broad scattering centered at 2θ ~25 o (Macromolecules,
1991, 24, 779, figure 3(a))
Page 34: grammar error
Reply: change ‘can be also’
To ‘can also be’
Trang 7Page 34: The examiner asks for more magnified SEM figures
Reply: not changed
Explanation: For better comparison, the SEM in Figure 2.5 are of the
same magnification (x15,000) as the SEM in Figure 2.6 and 2.7
Page 34: The examiner questions why the concentration of CTAB is low
Reply: add ‘(and meanwhile the low concentration of CTAB)’
Explanation: the concentration ratio of CTAB to HAuCl4 was kept
constant in the experiment, thus the concentration of CTAB was lowered
when the concentration of HAuCl4 decreased
Page 36: expression modification
Reply: change ‘different pressures’
To ‘different pressure levels’
Page 38: expression modification
Reply: delete ‘the’ in ‘at the atmospheric pressure’
Page 39: In comparison, the examiner asks for the conductivity value for
the PANI films at the reduced pressure
Reply: calculate the conductivity from the equation (1) σ = L/(S·R)
Trang 8Where σ is the conductivity, L is the length of the gap, S is the cross section is of the PANI film, and R is the resistance From Figure 2.8 the length L is around 1×10-5 m, and the cross section are S is 5×10-11 m2 From Figure 2.9 (c) the resistance R is around 2×109Ω from 3V to 4V Thus the value of conductivity is around 10-6 S/cm
Page 41: The examiner questions ‘why the 1166 cm-1 band is considered
as a measure of the degree of delocalization of electrons in PANI’
Reply: not changed
Explanation: According to the reference 51, the peak around 1140 cm-1 is assigned to the mode of Q=NH-B or B-N(+)H-B in the doped state After dedoping process, the structure changes to N=Q=N, and the peak position changes to around 1160 cm-1 accordingly Therefore, this band is reported (e.g in reference 52) to be the measurement of electron delocalization degree in PANI
Page 42: The examiner questions ‘why the strong peak centered at about
950 nm with a free-carrier tail extending into the near-infrared region is and indication PANI in doped state.’
Reply: not changed
Explanation: According to the reference 18, the band around 1000 nm is assigned to the polaron transition in doped PANI In reference 19, the
Trang 9position shifts lower to 800 nm when chloroaurate acid is used as the oxidant to synthesize doped PANI nanofibers More information can be
found in other references (Polymer 2006, 47, 5295 and Macromolecules
1995, 28, 2858)
Trang 10Chapter Three
Page 48: The examiner comments that the two paragraphs in 3.1 are
‘repeated’
Reply: not changed
Explanation: The paragraphs in 3.1 give an introduction of chemical
synthesis methods for PANI nanostructures Although some literatures are mentioned and cited in the first two chapters, they are discussed in detail and focused on the 2D structures in this Chapter
Page 50: The examiner comments that the paragraph in 3.2.1 is
‘repeated’
Reply: not changed
Explanation: In Chapter Three, trioctylmethylammonium chloride
(TOAC) is used as surfactants instead of cetyltrimethylammonium
bromide (CTAB) in Chapter Two; other chemicals remain the same
Page 52: The examiner comments that the paragraph in 3.2.4 is
‘repeated’
Reply: not changed
Explanation: The characterization methods are the same as those in
Chapter Two, but it is supposed as an integrated part in 3.2 Experimental
Section for clearer clarification
Trang 11Page 58: The examiner questions ‘why does PANI plate form’
Reply: not changed
Explanation: In 3.3.1.1 the experimental results are described first and the
assumption on the plate formation is clarified in the section ‘Reaction on glass’ (Page 61)
Page 60: The examiner question ‘glass beaker’
Reply: not changed
Explanation: The glass beaker used in my experiments is the simple glass container commonly used in laboratories
Page 60: The examiner question ‘Is there a way to predict the point of change’
Reply: Unfortunately, the exact point of morphology change can not be
predicated, this is why a lot of reactions were conducted under different conditions
Page 61: The examiner question ‘why PANI films were found adhered to substrates in acidic aqueous reactions’
Reply: not changed
Explanation: The acidic aqueous solution was traditionally adopted for
Trang 12aniline polymerization PANI films were found adhered to glass beakers (reference 38) and other substrates (reference 28 and 39) under such conditions
Page 61: The examiner question ‘epitaxial growth of PANI on the glass beaker wall’
Reply: not changed
Explanation: Epitaxial nucleation and growth refer to a film fabrication method, in which the deposited film takes on a lattice structure and orientation identical to those of the substrate In this thesis, ‘the epitaxial growth of PANI’ means that PANI grew following the orientation of the glass beaker wall and thus produced the 2D plate morphology
Page 63: grammar modification
Reply: change ‘even diffuse to’
To ‘evenly diffuse to’
Page 64: The examiner question: ‘Thus the initial acidity inside TOAC-HAuCl4 reverse micelles is much lowered.’
Reply: not changed
Explanation: Mass transfer is reported to happen between reverse micelles In my experiments, when HCl/TOAC solution was mixed into
Trang 13the HAuCl4/TOAC solution, protons were expected to transfer from HCl-TOAC reverse micelles into TOAC-HAuCl4, thus the acidity in the aqueous portion inside the reverse micelles would increase
Page 65: grammar error
Reply: change ‘in background’
To ‘in the background’
Page 65: The examiner question ‘how to determine Au contents are below 3% mass percents’
Reply: the additional figure 3.11 (e) is added
Explanation: The element distribution is reported in the form of mass percents in Energy-dispersive X-ray Spectra (EDX) results, which is added as Fig 3.11e
Trang 14Page 67: grammar error
Reply: change ‘a strong peak around 850 nm’
To ‘a strong peak at round 850 nm’
Trang 15Chapter Four
Page 76: The first paragraph in 4.1 is considered ‘repeated’
Reply: not changed
Explanation: The first paragraph gives a very brief introduction of different methods used to synthesize micro and nano structures of conducting polymers, which is closely related with the synthesis section
in this chapter
Page 76: The examiner question ‘reverse micelles in non-polar solvents’
Reply: not changed
Explanation: Compared with the direct micelle in aqueous solution water-in-oil micelle), the reverse micelle in non-polar solvent (such as toluene) forms an aggregate with the hydrophobic tail outside in contact with surrounding solvent and the hydrophilic head inside the micelle centre
Page 77: misunderstanding expression
Reply: change ‘It would therefore be interesting to investigate the
influence of surfactant type on the morphologies and electrical properties
of PANI’
To ‘It would therefore be interesting to investigate the influence of
surfactant type on the PANI morphologies and electrical properties.’
Trang 16Page 77: The examiner question ‘In contrast, no electrical property of 2D structures has been discussed23’
Reply: not changed
Explanation: In the reference 23, two-dimensional plate-like PANI is successfully synthesized, but no properties have been tested Thus electrical property was investigated on the prepared PANI plates
Page 77: format error
Reply: move the title ‘4.2 Experimental Section’ from the last line of
this page to the next page (Page 78)
Page 78: The paragraph in 4.2.1 is considered ‘repeated’
Reply: not changed
Explanation: This paragraph gives the chemicals used in the synthesis section, which is necessary in an independent chapter
Page 79: The examiner question ‘Figure 4.1 repeats Figure 3.7’
Reply: not changed
Explanation: The two figures have a slight difference In Figure 4.1, trioctylamine is used as the surfactant instead of trioctylmethylammonium chloride (TOAC) in Figure 3.7 This difference
Trang 17is marked on the top of Figure 4.1
Page 79: The paragraph in 4.2.4 is considered ‘repeated’
Reply: not changed
Explanation: This paragraph gives the methods used for characterizing PANI structures, which is necessary in an independent chapter
Page 80: expression modification
Reply: change ‘drop case on an insulating SiO2 substrate’
To ‘drop case onto an insulating SiO 2 substrate’
Page 80: The paragraph in 4.2.5 is considered ‘repeated’
Reply: not changed
Explanation: This paragraph gives the methods used for measuring the electrical properties of PANI films and individual structures, which is necessary in an independent chapter
Page 82: Figure 4.2 inset title error
Reply: change to ‘SEM images with an enlarged SEM inset (b) and
TEM insets (c, f) of the PANI micro and nano structures’
Page 83: Figure 4.3 inset title error
Trang 18Reply: change to ‘SEM images with an enlarged SEM inset (a) and
TEM insets (b, c) of the PANI micro and nano structures’
Page 84: The examiner question ‘the epitaxial growth of PANI’
Reply: not changed
Explanation: Epitaxial nucleation and growth refer to a film fabrication method, in which the deposited film takes on a lattice structure and orientation identical to those of the substrate In this thesis, ‘the epitaxial growth of PANI’ means that PANI grew following the orientation of the glass beaker wall and thus produced the 2D plate morphology
Page 84: grammar error
Reply: change ‘in the Chapter 3’
To ‘in Chapter 3’
Page 85: The examiner question ‘the last step of pick-and-place process’
Reply: not changed
Explanation: In references 58 and 59, ‘the pick-and-place process’ refers
to the processes of picking up and putting the nanostructures synthesized
in the first step to the prescribed positions
Trang 19Chapter Five
Page 98: grammar error
Reply: change ‘the main purpose of this study is to’
To ‘the main purpose of this study was to’