臺灣博碩士論文加值系統

影響誘電(SmC*)及反誘電性液晶(SmCＡ*)相的因素很多，像是旋光末端基團、硬核結構、連接基、非旋光末端烷鏈長度和光學純度等等。因而本研究為進一步了解改變液晶分子的非旋光烷鏈末端基團和硬核結構對於誘電以及反誘電性液晶相穩定度的關係，以一旋光性化合物 (S)-propylene oxide為起始物與半氟化的醇類進行開環反應得到化合物(S)-1-methyl-2-(2,2,3,3,4,4,4-heptafluorobutoxy) ethanol，並以此化合物為前驅物合成出四系列新型旋光液晶材料。主要藉由改變液晶分子的非旋光末端基團以及硬核結構研究且討論其對其液晶相及光電性質的影響。
合成的新型旋光液晶材料藉由偏光紋理圖及DSC的鑑定可分別得知液晶相及相轉移溫度的變化，再經由電流轉換行為及介電性質的量測可進一步鑑定誘電性液晶相的存在。
實驗結果顯示所有棒狀液晶化合物除了化合物III-2以外皆具有誘電性SmC*和反誘電性SmCA*液晶相。具有曲棍型硬核結構的液晶分子抑制了反誘電性SmCA*液晶相的生成，且所有曲棍型化合物都具有SmA*和SmC*液晶相。
改變化合物硬核結構和非旋光烷鏈末端基團使得液晶相產生差異，對棒狀液晶化合物的誘電性SmC*液晶相溫度範圍而言，隨硬核結構為PhPhCOONa > PhCOOPhPh > PhPhCOOPh > PhCOONa遞減，而末端基團為 hydroxyalkyl > acryloyl > propionyl > alkenyl > alkyl遞減，棒狀液晶化合物的反誘電性SmCA*液晶相溫度範圍隨硬核結構PhPhCOONa > PhCOONa > PhPhCOOPh > PhCOOPhPh遞減和末端基團為alkenyl > alkyl > acryloyl > propionyl遞減，而導入氫氧基團的液晶分子抑制了反誘電性SmCA*液晶相的生成。另外，曲棍型液晶化合物的誘電性SmC*液晶相溫度範圍則隨非旋光末端基團為alkenyl > acryloyl > alkyl > propionyl遞減而導入氫氧基團抑制了曲棍型化合物誘電性SmC*液晶相的生成。
藉由光電量測結果得知，曲棍型液晶化合物的自發性極化Ps值(15.39-49.59 nC/cm2)較棒狀液晶化合物小(83.21-130.00 nC/cm2)，導入萘環為硬核結構的棒狀液晶化合物其自發性極化Ps值(76.30-84.76 nC/cm2)比只含單苯或雙苯為硬核結構的棒狀液晶化合物小。棒狀液晶化合物導入不同的非旋光末端基團其自發性極化Ps值大小為hydroxyalkyl > alkenyl > alkyl ≒ acryloyl ≒ propionyl，推斷此結果是因為非旋光烷鏈末端基團影響分子極性。
四系列化合物的最大光學傾斜角分別為I(m=1-5) : 28.6∘-40.0∘, II(m=1-3) : 29.0∘-38.5∘, III(m=1-3) : 37.0∘-41.0∘以及IV(m=1-3) : 40.0∘-41.8∘，結果顯示改變分子非旋光烷鏈末端基團和硬核結構對光學傾斜角沒有明顯的關聯。


關鍵字: 棒狀化合物、曲棍型化合物、誘電性液晶、反誘電性液晶。

There are many factors affect the properties of ferroelectric (SmC*) and antiferroelectric (SmCA*) liquid crystal phase such as chiral terminal group, rigid core, linking group, terminal chain length and optical purity. For these reasons, the purpose of this research work is an attempt to correlate the various core structures and achiral terminal groups to the formation of mesomorphic phases, especially ferroelectric and antiferroelectric phases in chiral liquid crystal materials.
Thus, the chiral precursor, (S)-1-methyl-2-(2,2,3,3,4,4,4-heptafluorobutoxy) ethanol, was designed and synthesized by reacting (S)-propylene oxide with semi-fluorinated alcohol under basic condition. Consequently, four homologous series of chiral liquid crystal materials derived from this chiral precursor were prepared for the study.
The mesomorphic phases and their corresponding phase transition temperatures were primarily characterized by the microscopic textures and DSC thermograms, and the ferroelectric and antiferroelectric phases were further identified by the measurements of electric switching behavior and dielectric constant ε'.
The results show that rod-like compounds, with the exception of compound III-2 that exhibits N* and SmC* phases, possess both ferroelectric SmC* and antiferroelectric SmCA* phases. The compounds with bend-core structure suppress the formation of the antiferroelectric SmCA* phase and exhibit the phase sequence of Iso.-SmA*-SmC*-Cr..
The thermal stability of ferroelectric SmC* phase for the variation of the core structures in the rod-like compounds displays an order of PhPhCOONa > PhCOOPhPh > PhPhCOOPh > PhCOONa, and that for the variation of achiral terminal end group displays an order of hydroxyalkyl > acryloyl > propionyl > alkenyl > alkyl. Whereas, the thermal stability of antiferroelectric SmCA* phase for the variation of the core structures in the rod-like compounds displays an order of PhPhCOONa > PhCOONa > PhPhCOOPh > PhCOOPhPh, and that for the variation of achiral terminal end groups displays an order of alkenyl > alkyl > acryloyl > propionyl (hydroxyalkyl group suppresses the formation of the antiferroelectric SmCA* phase). For the bend-core compounds, the thermal stability of ferroelectric SmC* phase for the variation of achiral terminal end groups displays an order of alkenyl > acryloyl > alkyl > propionyl (hydroxyalkyl group suppresses the formation of the ferroelectric SmC* phase).
The electro-optical measurements show that the bend-core compounds have much lower Ps values (15.39-49.59 nC/cm2) as compared to the structurally similar compounds with the rod-like structure of the molecule(83.21-130.00 nC/cm2). And rod-like compounds composed of a naphthalene ring in the core structure of the molecule have the maximum Ps values (76.30-84.76 nC/cm2) lower than that composed of the phenyl or biphenyl ring in the core structure of the molecule. The measured maximum Ps values for the variation of achiral terminal functional groups in the rod-like compounds display an order of hydroxyalkyl > alkenyl > alkyl ≒ acryloyl ≒ propionyl at any temperature below Curie point. This may presumably due to the variation of the palarizability at the end group of achiral chain in the molecules.
The maximum optical tilt angles θ for four series of compounds are in the range of 28.6∘-40.0∘, 29.0∘-38.5∘, 37.0∘-41.0∘ and 40.0∘-41.8∘ for the corresponding compounds I(m=1-5), II(m=1-3), III(m=1-3) and IV(m=1-3). These results indicate that the measured optical tilt angles of the compounds in the ferroelectric and/or antiferroelectric phases have no significant correlation to the variations of achiral terminal groups in the molecules.

Keywords: Rod-like compound, bend-core compound, ferroelectric liquid crystal, antiferroelectric liquid crystal.

TABLE OF CONTENTS
ACKNOWLEDGEMENTS I
ENGLISH ABSTRACT II
中文摘要 V
TABLE OF CONTENTS VII
LIST OF SCHEME XI
LIST OF TABLES XII
LIST OF FIGURES XIII
CHAPTER 1 INTRODUCTION - 1 -
1.1. Overview - 1 -
1.2. Cholesteric (Ch) or chiral nematic (N*) phase - 2 -
1.3. Chiral smectic phases - 5 -
1.3.1. Chiral semectic A phase (SmA*) - 5 -
1.3.2. Chiral semectic C phase (Ferroelectic phase, SmC*) - 6 -
1.3.3. Antiferroelectric (SmCA*) phase - 10 -
1.3.3.1. Instruction - 10 -
1.3.3.2. Structure - 10 -
1.3.3.3. Antiferroelectric liquid crystal materials - 12 -
1.3.3.4. Electric-response switching behavior - 13 -
1.4. Motivation of study - 15 -
CHAPTER 2 EXPERIMENTAL - 19 -
2.1. Preparation of materials - 19 -
2.1.1. Synthesis of 4’-(10-undecenyloxy)biphenyl-4-carboxylic acid, 1 - 22 -
2.1.2. Synthesis of 4-[(methoxycarbonyl)oxy]benzoic acid, 2 - 22 -
2.1.3. Synthesis of (S)-1-methyl-2-(2,2,3,3,4,4,4-heptafluorobutoxy)ethanol, 3 - 23 -
2.1.4. Synthesis of (R)-1-methyl-2-(2,2,3,3,4,4,4-heptafluorobutoxy)ethyl 4-[(methoxycarbonyl)oxy]benzoate, 4 - 24 -
2.1.5. Synthesis of (R)-1-methyl-2-(2,2,3,3,4,4,4-heptafluorobutoxy)ethyl 4-hydroxybenzoate, 5 - 24 -
2.1.6. Synthesis of (R)-1-methyl-2-(2,2,3,3,4,4,4-heptafluorobutoxy)ethyl 4-{4-[4-(10-undecenyloxyphenyl)phenylcarbonyloxy]}benzoates, I-1 - 25 -
2.1.7. Synthesis of compounds I-2, I-3, I-4 and I-5 - 26 -
2.1.8. Synthesis of 4’-(11-hydroxyundecyloxy)biphenyl-4-carboxylic acid, 6 - 27 -
2.1.9. Synthesis of (R)-1-methyl-2-(2,2,3,3,4,4,4-heptafluorobutoxy)ethyl 4-{4-[4-(11-hydroxyundecyloxyphenyl)phenylcarbonyloxy]}benzoates, II-1 - 27 -
2.1.10. Synthesis of compounds II-2 and II-3 - 28 -
2.1.11. Synthesis of (R)-1-methyl-2-(2,2,3,3,4,4,4-heptafluorobutoxy)ethyl 4-{4-[4-(11-acryloyloxyundecyloxyphenyl)phenylcarbonyloxy]}benzoates, III-1 - 29 -
2.1.12. Synthesis of compounds III-2 and III-3 - 30 -
2.1.13. Synthesis of (R)-1-methyl-2-(2,2,3,3,4,4,4-heptafluorobutoxy)ethyl 4-{4-[4-(11-propionyloxyundecyloxyphenyl)phenylcarbonyloxy]}benzoates, IV-1 - 30 -
2.1.14. Synthesis of compounds IV-3 - 31 -
2.2. Characterization of Materials - 32 -
2.2.1. Chemical structure identification - 32 -
2.2.2. Mesophase identification - 32 -
2.2.3. Preparation of homogenous cells - 32 -
2.2.4. Alignment of liquid crystals in SSFLC Cells - 33 -
2.2.5. Measurements of switching behavior - 33 -
2.2.6. Dielectric constant measurement - 33 -
2.2.7. The spontaneous polarization (Ps) measurement - 34 -
2.2.8. Optical tilt angle measurement - 37 -
CHAPTER 3 RESULTS AND DISCUSSION - 38 -
3.1. Chemical structure identification - 38 -
3.1.1. Mesophase studies - 38 -
3.2. The effect of various core structures on the mesophases and electro-optical properties of chiral materials - 39 -
3.2.1.1. Phase Transition temperatures and mesomorphic properties of chiral compounds I-1, I-2, I-3, I-4 and I-5 - 39 -
3.2.1.2. Differential scanning calorimetric (DSC) studies for the compounds I-1~I-5 - 44 -
3.2.1.3. Switching current behavior studies for the compounds I-1, I-2, I-3, I-4 and I-5 - 49 -
3.2.1.4. Dielectric property (ε’) measurements for the compounds I-1, I-2, I-3, I-4 and I-5 - 51 -
3.2.1.5. Spontaneous polarization (Ps) measurements for the compounds I-1, I-2, I-3, I-4 and I-5 - 53 -
3.2.1.6. The optical tilt angle (θ) measurements for the compounds I-1, I-2, I-3, I-4 and I-5 - 53 -
3.2.2.1. Phase Transition temperatures and mesomorphic properties of chiral compounds II-1, II-2 and II-3 - 56 -
3.2.2.2. Differential scanning calorimetric (DSC) studies for the compounds II-1~II-3 - 57 -
3.2.2.3. Switching current behavior studies for the compounds II-1, II-2 and II-3 - 62 -
3.2.2.4. Spontaneous polarization (Ps) measurements for the compounds II-1, II-2 and II-3 - 64 -
3.2.2.5. The optical tilt angle (θ) measurements for the compounds II-1, II-2 and II-3 - 53 -
3.2.3.1. Phase Transition temperatures and mesomorphic properties of chiral compounds III-1, III-2 and III-3 - 67 -
3.2.3.2. Differential scanning calorimetric (DSC) studies for the compounds III-1~III-3 - 68 -
3.2.3.3. Switching current behavior studies for the compounds III-1, III-2 and III-3 - 73 -
3.2.3.4. Dielectric property (ε’) measurements for the compounds III-1, III-2 and III-3 - 75 -
3.2.3.5. Spontaneous polarization (Ps) measurements for the compounds III-1, III-2 and III-3 - 77 -
3.2.3.6. The optical tilt angle (θ) measurements for the compounds III-1, III-2 and III-3 - 77 -
3.2.4.1. Phase Transition temperatures and mesomorphic properties of chiral compounds IV-1 and IV-3 - 80 -
3.2.4.2. Differential scanning calorimetric (DSC) studies for the compounds IV-1 and IV-3 - 82 -
3.2.4.3. Switching current behavior studies for the compounds IV-1 and IV-3 - 85 -
3.2.4.4. Dielectric property (ε’) measurements for the compounds IV-1 and IV-3 - 87 -
3.2.4.5. Spontaneous polarization (Ps) measurements for the compounds IV-1 and IV-3 - 89 -
3.2.4.6. The optical tilt angle (θ) measurements for the compounds IV-1 and IV-3 - 89 -
3.3. The effect of various achiral terminal chains on the mesophases and electro-optical properties of chiral materials - 92 -
3.3.1. The comparison of mesomorphic properties with various achiral terminal groups - 93 -
3.3.1.1. The effect of compounds containing unsaturated double bond at achiral terminal chain on mesophase behaviors - 93 -
3.3.1.2. The effect of compounds containing hydroxyl functional group at achiral terminal chain on mesophase behaviors - 93 -
3.3.1.3. The effect of compounds containing acryloyl or propionyl group at achiral terminal chain on mesophase behaviors - 94 -
3.3.2. The comparison of spontaneous polarization (Ps) with various achiral terminal groups - 97 -
3.3.2.1. The effect of compounds changing achiral terminal chain from alkyl to alkenyl chain on the spontaneous polarization - 97 -
3.3.2.2. The effect of compounds containing hydroxyl functional group at achiral terminal chain on the spontaneous polarization - 97 -
3.3.2.3. The effect of compounds containing acryloyl or propionyl achiral terminal chain on the spontaneous polarization - 98 -
CHAPTER 4 CONCLUSIONS - 102 -
REFERENCES - 105 -
Appendix - 108 -

LIST OF SCHEME
Scheme 1 Synthetic procedures for the target compounds I-1, I-2, I-3, I-4 and I-5. - 20 -
Scheme 2 Synthetic procedures for the target compounds II-1, II-2, II-3, III-1, III-2, III-3, IV-1 and IV-3. - 21 -

LIST OF TABLES
Table 3.2.1.1 The phase transition temperatures T(℃) and enthalpies ΔH(KJ/mol) of the transition for the materials I-1, I-2, I-3, I-4 and I-5 measured by DSC at 5℃/min scanning rate on cooling stage. - 47 -
Table 3.2.2.1 The phase transition temperatures T(℃) and enthalpies ΔH(KJ/mol) of the transition for the materials II-1, II-2 and II-3 measured by DSC at 5℃/min scanning rate on cooling stage. - 61 -
Table 3.2.3.1 The phase transition temperatures T(℃) and enthalpies ΔH(KJ/mol) of the transition for the materials III-1, III-2 and III-3 measured by DSC at 5℃/min scanning rate on cooling stage. - 72 -
Table 3.2.4.1 The phase transition temperatures T(℃) and enthalpies ΔH(KJ/mol) of the transition for the materials IV-1 and IV-3 measured by DSC at 5℃/min scanning rate on cooling stage. - 84 -

LIST OF FIGURES
Figure 1.1 The melting process of a calamitic (rod-like) liquid-crystalline material [1]. - 3 -
Figure 1.2 Placement of the liquid crystal phase within the general scheme of the common states of matter. Two basic group of liquid crystals are distinguished: lyotropic phases, which form as a function of concentration c in the present of an isotropic solvent; and thermotropic phases, which are observed by variation of temperature T. Thermotropic phases are further classified according to their basic molecular shaped: rod-like (calamitic), disk-like (discotic), and lath-like (sanidic) [3]. - 3 -
Figure 1.3. Helical structure of the chiral nematic phase (N*) [1]. - 4 -
Figure 1.4 The structure of the smectic A (SmA*) phase [1]. - 5 -
Figure 1.5 Symmetry operations in the smectic C phase and chiral smectic C (SmC*) phase [1]. - 7 -
Figure 1.6 Helical macrostructure of the smectic C* phase [1]. - 8 -
Figure 1.7 Schematic representation of a "surface stabilized FLC" (SSFLC) cell where the helix is unwound due to the strong interaction in thin cell. The director of a molecule can be on either side of a cone with an opening angle of 2? and alternate each other by applying electrical field and vice versa. - 9 -
Figure 1.8 Helicoidal structures of the ferroelectric and antiferroelectric phases, and a local molecular arrangement in SmCA* [21]. - 11 -
Figure 1.9 Schematic illustration of the molecular orientational structures and the simulated light transmittance as function of electrical field in the three stable states. - 14 -
Figure 2.1 Block diagram for the measure circuit. - 36 -
Figure 2.2 Schematic illustrations for the current induced by applying a field with a triangular form. - 36 -
Figure 2.3 Schematic illustrations for the measurement of the apparent tilt angle. - 37 -
Figure 3.2.1.1 Texture of compound I-1 observed from polarizing microscope on cooling process (a) the focal-conic texture of SmA* phase (149.5℃, magnification × 400), (b) the striated focal-conic texture of SmC* phase (145.4℃, magnification × 400), (c) the broken focal-conic texture of SmCA* phase (136.5℃, magnification × 400) and (d) the texture of Cr. phase (41.6℃, magnification × 400). - 41 -
Figure 3.2.1.2 The microscopic texture of the SmCA* phase of I-1 at 126.6℃ taken with the material confined in a polyamide coated cell with spacing 2μm under crossed polarizing microscope (magnification × 400) (a) +6V (b) 0V (c) -6V. - 42 -
Figure 3.2.1.3 The microscopic texture of the SmCA* phase of I-2 at 101.8℃ taken with the material confined in a polyamide coated cell with spacing 2μm under crossed polarizing microscope (magnification × 400) (a) +6V (b) 0V (c) -6V. - 43 -
Figure 3.2.1.4 and 3.2.1.5 DSC thermograms for compound I-1 and I-2 on heating and cooling runs at a scanning rate of 5℃/min. - 46 -
Figure 3.2.1.6 A chart of phase transition temperature as a function of rigid core structure for the chiral materials I-1, I-2, I-3, I-4 and I-5 on cooling. - 48 -
Figure 3.2.1.7 The switching current behavior of compound I-2 at 20Hz of frequency and the amplitude of 5Vp-p in cell with 2µm thickness in the SmA*, SmC* and SmCA* phases at 133.4℃, 122.3℃ and 68.8℃, correspondingly. - 50 -
Figure 3.2.1.8 Temperature dependence of the dielectric constant ??S for the compound I-2 at 10kHz in the cell with 25?慆 thickness under 1℃/min. cooling process. - 52 -
Figure 3.2.1.9 Magnitudes of the spontaneous polarization plotted a function of temperature for (a) Compound I-1, (b) Compound I-2, (c) Compound I-3, (d) Compound I-4, and (e) Compound I-5. The Tc is the temperature of SmA*-SmC* or Iso.-SmC* transition. - 54 -
Figure 3.2.1.10 Temperature dependence of apparent tilt angle for the materials I-1, I-2, I-3, I-4 and I-5 in cell with 2μm thickness. The Tc is the temperature of SmA*-SmC* or Iso.- SmC* transition. - 55 -
Figure 3.2.2.1 Texture of compound II-1 observed from polarizing microscope on cooling process (a) the focal-conic texture of SmA* phase (136.3℃, magnification × 400), (b) the texture of SmA*-SmC* phase (129.8℃, magnification × 400), (c) the striated focal-conic texture of SmC* phase (129.7℃, magnification × 400), (d) the texture of SmC*-SmX1* phase (105.1℃, magnification × 400), (e) the unidentified focal-conic texture of SmX1* phase (93.0℃, magnification × 400) and (f) the texture of Cr. phase (86.6℃, magnification × 400). - 59 -
Figure 3.2.2.2 DSC thermograms for compound II-1 on heating and cooling runs at a scanning rate of 5℃/min. - 60 -
Figure 3.2.2.3 A chart of phase transition temperature as a function of rigid core structure for the chiral materials II-1, II-2 and II-3 on cooling. - 61 -
Figure 3.2.2.4 The switching current behavior of compound II-1 at 20Hz of frequency and the amplitude of 5Vp-p in cell with 2µm thickness in the SmA*, SmC*, SmX1* and Cr. phases at 131.5℃, 107.7℃, 103.3℃ and 81.7℃, correspondingly. - 63 -
Figure 3.2.2.5 Magnitudes of the spontaneous polarization plotted a function of temperature for (a) Compound II-1 and (b) Compound II-2. The Tc is the temperature of SmA*-SmC* or Iso.-SmC* transition. - 65 -
Figure 3.2.2.6 Temperature dependence of apparent tilt angle for the materials II-1 and II-2 in cell with 2μm thickness. The Tc is the temperature of SmA*-SmC* or Iso.- SmC* transition. - 66 -
Figure 3.2.3.1 Texture of compound III-1 and III-2 observed from polarizing microscope on cooling process (a) the striated focal-conic texture of SmC* phase (112.4℃, magnification × 400), (b) the striated focal-conic texture of SmC* phase (97.2℃, magnification × 400), (c) the broken focal-conic texture of SmCA* phase (90.7℃, magnification × 400), (d) the texture of Cr. phase (44.7℃, magnification × 400) and (e) the paramorphotic texture of N* phase (97.2℃, magnification × 400). - 70 -
Figure 3.2.3.2 DSC thermograms for compound III-2 on heating and cooling runs at a scanning rate of 5℃/min. - 71 -
Figure 3.2.3.3 A chart of phase transition temperature as a function of rigid core structure for the chiral materials III-1, III-2 and III-3 on cooling. - 72 -
Figure 3.2.3.4 The switching current behavior of compound III-2 at 20Hz of frequency and the amplitude of 5Vp-p in cell with 5µm thickness in the N*, SmC*, SmC* and Cr. phases at 97.02℃, 91.6℃, 48.3℃ and 36.7℃, correspondingly. - 74 -
Figure 3.2.3.5 Temperature dependence of the dielectric constant ??S for the compound III-2 at 100Hz in the cell with 25?慆 thickness under 1℃/min. cooling process. - 76 -
Figure 3.2.3.6 Magnitudes of the spontaneous polarization plotted a function of temperature for (a) Compound III-1, (b) Compound III-2 and (c) Compound III-3. The Tc is the temperature of SmA*-SmC* or Iso.-SmC* transition. - 78 -
Figure 3.2.3.7 Temperature dependence of apparent tilt angle for the materials III-1, III-2 and III-3 in cell with 2μm thickness. The Tc is the temperature of SmA*-SmC* or Iso.- SmC* transition. - 79 -
Figure 3.2.4.1 Texture of compound IV-3 observed from polarizing microscope on cooling process (a) the focal-conic texture of SmA* phase (58.8℃, magnification × 400), (b) the texture of SmA*-SmC* phase (54.7℃, magnification × 400), (c) the striated focal-conic texture of SmC* phase (47.1℃, magnification × 400) and (d) the texture of Cr. phase (23.0℃, magnification × 400). - 81 -
Figure 3.2.4.2 DSC thermograms for compound IV-3 on heating and cooling runs at a scanning rate of 5℃/min. - 83 -
Figure 3.2.4.3 A chart of phase transition temperature as a function of rigid core structure for the chiral materials IV-1 and IV-3 on cooling. - 84 -
Figure 3.2.4.4 The switching current behavior of compound IV-3 at 20Hz of frequency and the amplitude of 5Vp-p in cell with 5µm thickness in the SmA*, SmC*, SmC* and Cr. phases at 56.1℃, 51.1℃, 34.0℃ and 27.0℃, correspondingly. - 86 -
Figure 3.2.4.5 Temperature dependence of the dielectric constant ??S for the compound IV-3 at 100Hz in the cell with 25?慆 thickness under 1℃/min. cooling process. - 88 -
Figure 3.2.4.6 Magnitudes of the spontaneous polarization plotted a function of temperature for (a) Compound IV-1 and (b) Compound IV-3. The Tc is the temperature of SmA*-SmC* or Iso.-SmC* transition. - 90 -
Figure 3.2.4.7 Temperature dependence of apparent tilt angle for the materials IV-1 and IV-2 in cell with 2μm thickness. The Tc is the temperature of SmA*-SmC* or Iso.- SmC* transition. - 91 -
Figure 3.3.1 A chart of phase transition temperature as a function of achiral terminal chains for the chiral materials i-1, I-1, II-1, III-1 and IV-1 on cooling. - 95 -
Figure 3.3.2 A chart of phase transition temperature as a function of achiral terminal chains for the chiral materials i-3, I-3, II-3, III-3 and IV-3 on cooling. - 96 -
Figure 3.3.3 Magnitudes of the spontaneous polarization plotted a function of temperature for (a) Compound i-1, (b) Compound i-3, (c) Compound i-4, (d) Compound I-1, (e) Compound I-3 and (f) Compound I-4. The Tc is the temperature of SmA*-SmC* or Iso.-SmC* transition. - 99 -
Figure 3.3.4 Magnitudes of the spontaneous polarization plotted a function of temperature for (a) Compound II-1 and (b) Compound II-2. The Tc is the temperature of SmA*-SmC* or Iso.-SmC* transition. - 100 -
Figure 3.3.5 Magnitudes of the spontaneous polarization plotted a function of temperature for (a) Compound i-1, (b) compound III-1 and (c) Compound IV-1. The Tc is the temperature of SmA*-SmC* or Iso.-SmC* transition. - 101 -

REFERENCES
[1] D. Demus, J. W. Goodby, G. W. Gray, H. W. Spiess, V. Vill. Handbook of Liquid Crystals, 2(A), 3 (1998).
[2] F. Reinitzer. Monatsh. Chem., 9, 421 (1888).
[3] I. Dierking, Textures of Liquid Crystals. (Wiley-VCH) (2003).
[4] R.B. Meyer, L. Liebert, L. Strzelecki, P. Keller. J. Phys. Lett., 36, L69 (1975).
[5] A.D.L. Chandani, Y. Ouchi, H. Takezoe, A. Fukuda, K. Terashima, K. Furukawa, A. Kishi. Jpn. J. Appl. Phys., 28, L1261 (1989).
[6] A.D.L. Chandani, T. Hagiwara, Y. Suzuki, Y. Ouchi, H. Takezoe, A. Fukuda. Jpn. J. Appl. Phys., 27, L729 (1988).
[7] E. Gorecka, A.D.L. Chanani, Y. Ouchi, H. Takezoe, A. Fukuda. Jpn. J. Appl. Phys., 29, 131 (1990).
[8] J. W. Goodby, M. A. Waugh, S. M. Stein, E. Chin, R. Pindak, J. S. Patel. J. Am. Chem. Soc., 111, 8119 (1989).
[9] L. J. Yu, H. Lee, C. S. Bak, M. M. Labes., Phys. Rev. Lett., 36, 388 (1976).
[10] N. A. Clark, S. T. Lagerwall. Appl. Phys. Lett., 36, 899 (1980).
[11] M. Yamawaki, Y. Yamada, N. Yamamoto, K. Mori, H. Hayashi, Y. Suzuki, Y. S. Negi, T. Hagiwara, I. Kawamura, H. Orihara, Y. Ishibahsi. Jpn. Display '89, 26 (1989).
[12] J. Johno, A. D. L. Chandani, J. Lee, Y. Ouchi, H. Takezoe, A. Fukuda, K. Ioth, T. Kitazume. Proc. Jpn. Display, 22 (1989).
[13] Z. Lehmann. Phys. Chem., 4, 462 (1889).
[14] S. Garoff, R.B. Meyer. Phys. Rev. Lett., 38, 848 (1977).
[15] S. Garoff, R.B. Meyer. Phys. Rev. A, 19, 338 (1979).
[16] D. Demus, J. W. Goodby, G. W. Gray, H. W. Spiess, V. Vill. Handbook of Liquid Crystals, 2(A), 127 (1998). (Wiley-VCH)
[17] D. Demus, J. W. Goodby, G. W. Gray, H. W. Spiess, V. Vill. Handbook of Liquid Crystals, 1, 118 (1998).
[18] Y. Takanishi, H. Takezoe, A. Fukuda, H. Komura, J. Watanabe., Liq. Cryst., 2, 71 (1992).
[19] A.D.L. Chandani, T. Hagiwara, Y. Suzuki, Y. Ouchi, H. Takezoe, A. Fukuda. Jpn. J. Appl. Phys., 27, L729 (1988).
[20] K. Hiraoka, A. Taguchi, Y. Ouchi, H. Takezoe, A. Fukuda. Jpn. J. Appl. Phys., 29, L103 (1990).
[21] A. Fukuda, Y. Takanishi, T. Isozaki, K. Ishikawa, H. Takezoe. J. Mater. Chem., 4, 997 (1994).
[22] This compound had already been reported as an FLC by T. Inukai, K. Furukawa, K. Terashima, S. Saitoh, M. Isogai, T. Kitamura, A. Mukoh at the 11th Japanese Liquid Crystal Conference (Kanazawa, 1985). See its Abstract 2N22 on p.172 (in Japanese).
[23] N. Hiji, A.D.L. Chandani, S. Nishiyama, Y. Ouchi, H. Takezoe, A. Fukuda. Ferroelectrics, 85, 99 (1988).
[24] K. Furukawa, K. Terashima, M. Ichihashi, S. Saitoh, K. Miyazawa, T. Inukai. Ferroelectrics, 85, 451 (1988).
[25] H.S. Kitzerow, C. Bahr. Chirality in Liquid Crystals, p.251 reference therein (2001). (Springer).
[26] Y. Suzuki, O. Nonaka, N. Okabe, T. Hagiwara, I. Kawamura, N. Yamamoto, Y. Yamada, T. Kitazume. Ferroelectrics, 147, 109 (1993).
[27] D. Demus, J.W. Goodby, G. W. Gray, H.W. Spiess, V. Vill. Handbook of Liquid Crystals, 2(B), p.684-688 (1998). (Wiley-VCH)
[28] A. D. L. Chandani, E. Gorecka, Y. Ouchi, H. Takezoe, A. Fukuda. Jpn. J. Appl. Phys., 28, L1265 (1989).
[29] H. Takezoe, J. Lee, A. D. L. Chandani, E. Gorecka, Y. Ouchi, A. Fukuda, K. Terashima, K. Furukawa. Ferroelectrics, 114, 187 (1991).
[30] H. Hayashi, M. Takemura, K. Kikuchi, Y. Hijikata, H. Orihara, Y. Ishibashi. Jpn. J. Appl. Phys., 31, 3182 (1992).
[31] Y. Suzuki, T. Hagiwara, I. Kawamura. Liq. Cryst., 6, 2, 167 (1989).
[32] Y. Suzuki, O. Nonaka, N. Okabe, T. Hagiwara, I. Kawamura, N. Yamamoto, Y. Yamada, T. Kitazume. Ferroelectrics, 147, 109 (1996).
[33] S.-L. Wu, C.-Y. Lin. Liq. Cryst., 33, 5, 537 (2006).
[34] S.-L. Wu, C.-Y. Lin. Liq. Cryst., 32, 8, 1053 (2005).
[35] M.-P. Kao. Dissertation for Master Degree, Tatung University (2005).
[36] Y.-F. Li. Dissertation for Master Degree, Tatung University (2007)
[37] K. Miyasato, S. Abe, H. Takezoe, A. Fukuda, E. Kuze. Jpn. J. Appl. Phys., 22, L661 (1983).
[38] S. Wrobrl, W. Haase, M. Pfeiffer, L. Beresnev, T. Geelhaar. Mol. Cryst. Liq. Cryst., 212, 335 (1992).
[39] T. R. Taylor, J. R. Fergasson, S. L. Arora. Phys. Rev. Lett., 194, 359 (1970).
[40] L. M. Blinov, V. A. Baikalov, M. I. Barnik, L. A. Beresnev, E. P. Pozhidaev, S. A. Yablonsky. Liq. Cryst., 2, 121 (1987).
[41] A. J. Slaney, M. Watson, J. W. Goodby. J. Mater. Chem., 5, 2145 (1995).
[42] A. Fukuda, Y. Takanishi, T. Isozaki, K. Ishikawa, H. Takezoe, J. Mater. Chem., 4, 997 (1994).
[43] F. Gouda, K. Skarp, S. T. Lagerwall. Ferroelectrics. 113, 165 (1991).

[44] H. Takezoe, K. Hiraoka, T. Isozaki, K. Miyachi, H. Aoki, A. Fukuda. Modern Topics in Liquid Crystal-From Neutron Scattering to Ferroelectricity-World Scientific, 319 (1993).
[45] Y. Aoki, H. Nohira. Liq. Cryst., 23, 1, 87 (1997).
[46] S.-C. Huang. Dissertation for Master Degree, Tatung University (2010).
[47] S. J. Cowling, A.W. Hall, J. W. Goodby. Liq. Cryst., 32, 11, 1483 (2005).