Next generation of conducting materials for organic electronics 2

Summary 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. 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 ‘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 Reply: 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’ Page 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’ To ‘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’ Chapter 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 1991, 24, 779, figure 3(a)). Page 34: grammar error Reply: change ‘can be also’ To ‘can also be’ o (Macromolecules, Page 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) Where 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 position 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). Chapter 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. Page 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 aniline 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 the 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. Page 67: grammar error Reply: change ‘a strong peak around 850 nm’ To ‘a strong peak at round 850 nm’ Chapter 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.’ Page 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 is 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 SiO2 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 Reply: 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. Chapter Five Page 98: grammar error Reply: change ‘the main purpose of this study is to’ To ‘the main purpose of this study was to’ [...]... 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.’ Page 77: The examiner question ‘In contrast, no electrical property of 2D structures has been discussed23’ Reply: not changed... insulating SiO2 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... 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... instead of trioctylmethylammonium chloride (TOAC) in Figure 3.7 This difference is 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 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 aniline polymerization... 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... (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... 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... distribution is reported in the form of mass percents in Energy-dispersive X-ray Spectra (EDX) results, which is added as Fig 3.11e Page 67: grammar error Reply: change ‘a strong peak around 850 nm’ To ‘a strong peak at round 850 nm’ Chapter 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... 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 ... 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... the oxidant to synthesize doped PANI nanofibers More information can be found in other references (Polymer 20 06, 47, 529 5 and Macromolecules 1995, 28 , 28 58) Chapter Three Page 48: The examiner... plethora of analytes are reported to be detected,130-1 42 which are classified into one or more of the five established mechanisms.130 ‘ To ‘A plethora of analytes have already been reported.130-142