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Volume IV: Materials Systems and Applications II

Content
10. NANOMECHANISM OF THE HEXAGONAL-CUBIC PHASE TRANSITION IN BORON NITRIDE UNDER HIGH PRESSURE AT HIGH TEMPERATURE ---------------------------------------------------------------------------------------------------- 1 10.1 INTRODUCTION ------------------------------------------------------------------------------------------------------------------------------ 1 10.2 PROCESSING METHOD TO GET C-BN ----------------------------------------------------------------------------------------------------- 2 10.3 CHARACTERIZATION METHOD ------------------------------------------------------------------------------------------------------------ 3 10.4 PHASE TRANSITION OF BORON NITRIDE ------------------------------------------------------------------------------------------------- 4 10.4.1 Nanostructure of the Starting Material -------------------------------------------------------------------------------------------- 4 10.4.2 Phases and Nanostructures Appearing during the Hexagonal-Cubic Transition--------------------------------------------- 5 11.1 GENERAL OVERVIEW OF BATTERIES AND FUEL CELLS ------------------------------------------------------------------------------- 19 11.1.1 Introduction-------------------------------------------------------------------------------------------------------------------------- 19 11.1.2 An Overview of Batteries----------------------------------------------------------------------------------------------------------- 20 11.1.3 An Overview of Fuel Cells --------------------------------------------------------------------------------------------------------- 24 11.1.4 Importance of Nanomaterials in Batteries and Fuel Cells--------------------------------------------------------------------- 26 10.5 MECHANISM OF HEXAGONAL-CUBIC TRANSITION ----------------------------------------------------------------------------------- 27 10.5.1 Model for the Transition Mechanism--------------------------------------------------------------------------------------------- 27 10.5.2 Atomic Movement during the Conversion from w-to c-BN -------------------------------------------------------------------- 30 10.5.3 Facilitation of Synthesis of c-BN by Mechanochemical Effect---------------------------------------------------------------- 30 10.6 PROSPECT ---------------------------------------------------------------------------------------------------------------------------------- 33 10.7 CONCLUSIONS ----------------------------------------------------------------------------------------------------------------------------- 34 References------------------------------------------------------------------------------------------------------------------------------------ 35 13.2 SYNTHETIC STRATEGIES FOR VARIOUS NANOTUBE ARCHITECTURES -------------------------------------------------------------- 36 13.2.1 Chemical Vapor Deposition ------------------------------------------------------------------------------------------------------- 36 13.2.2 Growth of Self-oriented Multi-walled Nanotubes------------------------------------------------------------------------------- 37 13.2.3 Enable the Growth of Single-Walled Nanotubes by CVD---------------------------------------------------------------------- 38 13.2.4 Growth Mechanism of SWNT------------------------------------------------------------------------------------------------------ 40 13.2.5 Growth of Isolated Single-Walled Nanotubes on Controlled Surface Sites-------------------------------------------------- 41 13.2.6 Growth of Suspended SWNTs with Directed Orientations --------------------------------------------------------------------- 43 11. NANOMATERIALS FOR ENERGY STORAGE: BATTERIES AND FUEL CELLS---------------------------------------- 46 11.1 GENERAL OVERVIEW OF BATTERIES AND FUEL CELLS ------------------------------------------------------------------------------- 46 11.1.1 Introduction-------------------------------------------------------------------------------------------------------------------------- 46 11.1.2 An Overview of Batteries----------------------------------------------------------------------------------------------------------- 46 11.1.3 An Overview of Fuel Cells --------------------------------------------------------------------------------------------------------- 50 11.1.4 Importance of Nanomaterials in Batteries and Fuel Cells--------------------------------------------------------------------- 52 11.2 BATTERIES AND NANOMATERIALS ------------------------------------------------------------------------------------------------------ 53 11.2.1 Classifications of Advanced Batteries -------------------------------------------------------------------------------------------- 53 11.2.2 Major Components of Batteries --------------------------------------------------------------------------------------------------- 56 11.2.3 Applications of Nanomaterials in Advanced Batteries ------------------------------------------------------------------------- 58 11.2.4 Most Recent Developments -------------------------------------------------------------------------------------------------------- 63 11.3 FUEL CELLS AND NANOMATERIALS ----------------------------------------------------------------------------------------------------- 63 11.3.1 Classifications of Fuel Cell Systems---------------------------------------------------------------------------------------------- 64 11.3.2 Major Components and Nanomaterials in Fuel Cells-------------------------------------------------------------------------- 66
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11.3.3 Applications of Nanomaterials in Fuel Cells ------------------------------------------------------------------------------------ 67 11.3.4 Summary ----------------------------------------------------------------------------------------------------------------------------- 75 11.4 CONCLUSIONS ----------------------------------------------------------------------------------------------------------------------------- 75 References------------------------------------------------------------------------------------------------------------------------------------ 76 12. NANOCOMPOSITES---------------------------------------------------------------------------------------------------------------------- 85 12.1 INTRODUCTION ---------------------------------------------------------------------------------------------------------------------------- 85 12.2 GENERAL FEATURES OF NANOCOMPOSITES ------------------------------------------------------------------------------------------- 90 12.2.1 Physical Sensitivity: Three Effects of Nanoparticles on Material Properties ----------------------------------------------- 90 12.2.2 Chemical Reactivity ---------------------------------------------------------------------------------------------------------------- 91 12.2.3 Promising Improvements in Nanocomposites ----------------------------------------------------------------------------------- 92 12.2.4 Origin of Nanophases and Generating Stages ---------------------------------------------------------------------------------- 93 12.3 CERAMIC-BASED NANOCOMPOSITES --------------------------------------------------------------------------------------------------- 95 12.3.1 Strength Improvement of Ceramic-Based Nanocomposites ------------------------------------------------------------------- 96 12.3.2 Toughening Effect of Nanoceramic Composites ------------------------------------------------------------------------------- 101 12.3.3 Improvements of Nanoceramic Composites on Hardness and Wear -------------------------------------------------------- 102 12.3.4 Superplasticity of Ceramic Nanocomposites ----------------------------------------------------------------------------------- 103 12.3.5 Improvement of Nanoceramic Composites on Creep-------------------------------------------------------------------------- 104 12.3.6 Ceramic-Based Nanometallic Composites ------------------------------------------------------------------------------------- 104 12.4 METALLIC-BASED NANOCOMPOSITES ------------------------------------------------------------------------------------------------- 105 12.5 POLYMER-BASED NANOCOMPOSITES ------------------------------------------------------------------------------------------------- 106 12.6 SUMMARIES OF NANOCOMPOSITES ---------------------------------------------------------------------------------------------------- 108 References----------------------------------------------------------------------------------------------------------------------------------- 109 13. GROWTH AND PROPERTIES OF SINGLE-WALLED NANOTUBES------------------------------------------------------- 111 13.1 INTRODUCTION --------------------------------------------------------------------------------------------------------------------------- 111 13.2 SYNTHETIC STRATEGIES FOR VARIOUS NANOTUBE ARCHITECTURES ------------------------------------------------------------- 112 13.2.1 Chemical Vapor Deposition ------------------------------------------------------------------------------------------------------ 112 13.2.2 Growth of Self-oriented Multi-walled Nanotubes------------------------------------------------------------------------------ 113 13.2.3 Enable the Growth of Single-Walled Nanotubes by CVD--------------------------------------------------------------------- 114 13.2.4 Growth Mechanism of SWNT----------------------------------------------------------------------------------------------------- 116 13.2.5 Growth of Isolated Single-Walled Nanotubes on Controlled Surface Sites------------------------------------------------- 117 13.2.6 Growth of Suspended SWNTs with Directed Orientations -------------------------------------------------------------------- 119 13.3 PHYSICS IN ATOMICALLY WELL-DEFINED NANOWIRES ----------------------------------------------------------------------------- 121 13.3.1 Integrated Circuits of Individual Single-Walled Nanotubes ------------------------------------------------------------------ 121 13.3.2 Electron Transport Properties of Metallic Nanotubes ------------------------------------------------------------------------ 123 13.3.3 Electron Transport Properties of Semiconducting Nanotubes --------------------------------------------------------------- 125 13.3.4 Electron Transport Properties of Semiconducting Nanotubes with Small Band Gaps ------------------------------------ 128 13.4 INTEGRATED NANOTUBE DEVICES ----------------------------------------------------------------------------------------------------- 135 13.4.1 Nanotube Molecular Transistors with High Gains ---------------------------------------------------------------------------- 135 13.5 CONCLUSIONS ---------------------------------------------------------------------------------------------------------------------------- 137 References----------------------------------------------------------------------------------------------------------------------------------- 138 14. NANOMATERIALS FROM LIGHT-ELEMENT COMPOSITES -------------------------------------------------------------- 142 14.1 INTRODUCTION --------------------------------------------------------------------------------------------------------------------------- 142
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14.2 THEORETICAL PREDICTION ------------------------------------------------------------------------------------------------------------- 142 14.2.1 Empirical Model ------------------------------------------------------------------------------------------------------------------- 142 14.2.2 First-Principles Study ------------------------------------------------------------------------------------------------------------- 143 14.3 SYNTHESIS BY CHEMICAL VAPOR DEPOSITION (CVD) ------------------------------------------------------------------------------ 144 14.3.1 Bias-Assisted Hot Filament CVD ------------------------------------------------------------------------------------------------ 145 14.3.2 Electron Cyclotron Resonance Microwave Plasma-Assisted CVD (MPCVD) --------------------------------------------- 146 14.4 UNIFORM SIZE-CONTROLLED NANOCRYSTALLINE DIAMOND FILMS -------------------------------------------------------------- 147 14.4.1 Deposition with CN4/N2 Precursor ---------------------------------------------------------------------------------------------- 148 14.4.2 Influence of Additional H2 on Microstructure ---------------------------------------------------------------------------------- 151 14.4.3 Nitrogen Incorporation ----------------------------------------------------------------------------------------------------------- 153 14.4.4 Surface Stable Growth Model ---------------------------------------------------------------------------------------------------- 153 14.4.5 Field Electron Emission and Transport Tunneling Mechanism -------------------------------------------------------------- 154 14.5 NANOCRYSTALLINE CARBON NITRIDE FILMS ---------------------------------------------------------------------------------------- 156 14.5.1 α and β Structures------------------------------------------------------------------------------------------------------------------ 156 14.5.2 Tetragonal Structure --------------------------------------------------------------------------------------------------------------- 158 14.5.3 Monoclinic Structure -------------------------------------------------------------------------------------------------------------- 158 14.5.4 Fullerene-like Structure ----------------------------------------------------------------------------------------------------------- 159 14.5.5 Carbon Nitride/Diamond/Silicon Layers --------------------------------------------------------------------------------------- 159 14.5.6 Physical and Chemical Properties----------------------------------------------------------------------------------------------- 160 14.6 NANOCRYSTALLINE SILICON CARBONITRIDE FILMS --------------------------------------------------------------------------------- 161 14.6.1 Deposition with Nitrogen and Methane ----------------------------------------------------------------------------------------- 162 14.6.2 Deposition with Nitrogen, Methane and Hydrogen: Influence of Hydrogen Flow Ratio --------------------------------- 164 14.6.3 Lattice-Matched Growth Model-------------------------------------------------------------------------------------------------- 165 14.7 TURBOSTRATIC BORON CARBONITRIDE FILMS --------------------------------------------------------------------------------------- 166 14.7.1 Morphology and Composition --------------------------------------------------------------------------------------------------- 166 14.7.2 Turbostratic Structure ------------------------------------------------------------------------------------------------------------- 167 14.7.3 Raman and Photoluminescence -------------------------------------------------------------------------------------------------- 169 14.7.4 Field Electron Emission----------------------------------------------------------------------------------------------------------- 170 14.8 POLYMERIZED NITROGEN-INCORPORATED CARBON NANOBELLS ----------------------------------------------------------------- 171 14.8.1 Polymerized Nanobell Structure ------------------------------------------------------------------------------------------------- 171 14.8.2 Chemical Separation and Application ------------------------------------------------------------------------------------------ 172 14.8.3 Wall-Side Field Emission Mechanism------------------------------------------------------------------------------------------- 173 14.9 HIGHLY ORIENTED BORON CARBONITRIDE NANOFIBERS --------------------------------------------------------------------------- 175 14.9.1 Microstructure and Composition ------------------------------------------------------------------------------------------------ 175 14.9.2 Field Electron Emission----------------------------------------------------------------------------------------------------------- 176 14.10 CONCLUSIONS -------------------------------------------------------------------------------------------------------------------------- 177 References----------------------------------------------------------------------------------------------------------------------------------- 178 15,SELF ASSEMBLED ORDERED NANOSTRUCTURES ------------------------------------------------------------------------ 183 15.1 ORDERED SELF-ASSEMBLED NANOCRYSTALS --------------------------------------------------------------------------------------- 183 15.1.1 Processing of Nanocrystals for Self-Assembly --------------------------------------------------------------------------------- 185 15.1.2 Technical Aspects of Self-Assembling ------------------------------------------------------------------------------------------- 189 15.1.3 Structure of the Nanocrystal Self-Assembly ------------------------------------------------------------------------------------ 193 15.1.4 Properties of the Nanocrystal Self-Assembly----------------------------------------------------------------------------------- 198 15.2 ORDERED SELF-ASSEMBLY OF MESOPOROUS MATERIALS -------------------------------------------------------------------------- 202
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15.2.1 Processing -------------------------------------------------------------------------------------------------------------------------- 203 15.2.2 The Formation Mechanisms ------------------------------------------------------------------------------------------------------ 204 15.2.3 Applications ------------------------------------------------------------------------------------------------------------------------ 208 15.2.4 Mesoporous Materials of Transition Metal Oxides---------------------------------------------------------------------------- 212 15.3 HIERARCHICALLY STRUCTURED NANOMATERIALS ---------------------------------------------------------------------------------- 213 15.4 SUMMARY -------------------------------------------------------------------------------------------------------------------------------- 215 References----------------------------------------------------------------------------------------------------------------------------------- 216 16, MOLECULARLY ORGANIZED NANOSTRUCTURAL MATERIALS ------------------------------------------------------ 221 16.1 INTRODUCTION --------------------------------------------------------------------------------------------------------------------------- 221 16.1.1 Nanostructural Materials in Energy Sciences---------------------------------------------------------------------------------- 221 16.1.2 Nanophase Materials in Environmental and Health Sciences --------------------------------------------------------------- 221 16.1.3 Molecularly Organized Nanostructural Materials ---------------------------------------------------------------------------- 222 16.2 MOLECULARLY DIRECTED NUCLEATION AND GROWTH, AND MATRIX MEDIATED NANOCOMPOSITES ------------------------ 222 16.2.1 Molecularly Directed Nanoscale Materials in Nature ------------------------------------------------------------------------ 222 16.2.2 Directed Nucleation and Growth of Thin Films-------------------------------------------------------------------------------- 223 16.2.3 Matrix Mediated Nanocomposites ----------------------------------------------------------------------------------------------- 227 16.3 SURFACTANT DIRECTED HYBRID NANOSCALE MATERIALS ------------------------------------------------------------------------ 231 16.3.1 Ordered Nanoporous Materials -------------------------------------------------------------------------------------------------- 232 16.3.2 Hybrid Nanoscale Materials ----------------------------------------------------------------------------------------------------- 237 16.4 SUMMARY AND PROSPECTS ------------------------------------------------------------------------------------------------------------- 243 References----------------------------------------------------------------------------------------------------------------------------------- 243 17, NANOSTRUCTURED BIO-INSPIRED MATERIALS ---------------------------------------------------------------------------- 246 17.1 INTRODUCTION --------------------------------------------------------------------------------------------------------------------------- 246 17.2 CASE STUDY I: TEETH ------------------------------------------------------------------------------------------------------------------- 248 17.2.1 Control over Mineralization at Nanometer Scale------------------------------------------------------------------------------ 249 17.2.2 Hierarchical Structure in Biological Materials -------------------------------------------------------------------------------- 252 17.3 CASE STUDY II: MESOSCOPIC SILICA FILMS ------------------------------------------------------------------------------------------ 254 17.3.1 Hierarchical Film Structure ------------------------------------------------------------------------------------------------------ 256 17.3.2 Towards Control of the Properties ----------------------------------------------------------------------------------------------- 262 17.4 CONCLUSION ----------------------------------------------------------------------------------------------------------------------------- 262 References----------------------------------------------------------------------------------------------------------------------------------- 263 18, NANOPHASE METAL OXIDE MATERIALS FOR ELECTROCHROMIC DISPLAYS---------------------------------- 266 18.1 INTRODUCTION --------------------------------------------------------------------------------------------------------------------------- 266 18.2 BASIC CONCEPTS IN ELECTROCHROMISM--------------------------------------------------------------------------------------------- 267 18.2.1 Electrochromic Display Device -------------------------------------------------------------------------------------------------- 267 18.2.2 Electrochromic Materials--------------------------------------------------------------------------------------------------------- 268 18.2.3 Perceived Color and Contrast Ratio -------------------------------------------------------------------------------------------- 270 18.2.4 Coloration Efficiency and Response Time -------------------------------------------------------------------------------------- 270 18.2.5 Write-Erase Efficiency and Cycle Life ------------------------------------------------------------------------------------------ 270 18.3 NANOPHASE METAL OXIDE ELECTROCHROMIC MATERIALS ----------------------------------------------------------------------- 271 18.3.1 Synthesis of Supported ATO Nanocrystallites ---------------------------------------------------------------------------------- 272 18.3.2 Characterization of Supported ATO Nanocrystallites------------------------------------------------------------------------- 273
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6 SUMMARY -------------------------------------------------------------------------------------------------------------------------------.2.7. Wang. et al.1 Design Strategy -------------------------------------------------------------------------------------------------------------------. e.5 Direct THG (Feng.6 NONLINEAR OPTICAL FREQUENCY CONVERSION IN 1-D QPDSLS ---------------------------------------------------------------.1 INTRODUCTION --------------------------------------------------------------------------------------------------------------------------. et al.318 19.279 18. 1993a.6.276 18.332 V . c. Wang.6.2 Theoretical Treatment of the Nonlinear Optical Processes in QPDSLs ---------------------------------------------------. 1994.316 19.8 OUTLOOK --------------------------------------------------------------------------------------------------------------------------------. b.311 19.303 19. 1994.278 18. Qin. 1989) --------------------------------------------------------------------. 1990.6.292 18.282 18.326 References----------------------------------------------------------------------------------------------------------------------------------.5.3 OUTLINE OF THE NONLINEAR OPTICS ------------------------------------------------------------------------------------------------.. 1997a.325 19.4.6. 1996b) -----------------------------------------------------------------------------------------------------------------------------------------------.308 19. 1996c) -------------------------------------------------..2 Effect of Annealing Temperature on Contrast Ratio--------------------------------------------------------------------------. 1999) ---------------------------------------------.300 19..4. 1995..4 QPM Multiwavelength SHG (Zhu.2 Materials Selection ---------------------------------------------------------------------------------------------------------------.4 CONSTRUCTION OF PRINTED.7.275 18.4 A New Type of Optical Bistability Mechanism: Nonlinear Case with Two Incident Waves (Chen.317 19.2 PREPARATION OF DSLS ----------------------------------------------------------------------------------------------------------------. et al.3 Display Examples-----------------------------------------------------------------------------------------------------------------. d.300 19..1 Effect of Antimony Doping on Contrast Ratio---------------------------------------------------------------------------------.6.7.1 The Construction of QPDSL-----------------------------------------------------------------------------------------------------.4 WAVE VECTOR CONSERVATION --------------------------------------------------------------------------------------------------------.5 CONTRAST OF PRINTED ELECTROCHROMIC DISPLAYS USING ATO NANOPHASE MATERIALS ---------------------------------..3 Other Factors That Affect the Contrast Ratio ---------------------------------------------------------------------------------.310 19.301 19.1 Preparation of DSLs by Modulation of Ferroelectric Domains ------------------------------------------------------------.5.300 19.4.7.317 19. et al. 1999) ------------------------------------------------.321 19.320 19.7 OPTICAL BISTABILITY IN A 2-D DSL -------------------------------------------------------------------------------------------------.310 19. b. 1998.297 19. 1990. FLEXIBLE DISPLAYS USING INTERDIGITATED ELECTRODES -------------------------------------. Zhu.297 References----------------------------------------------------------------------------------------------------------------------------------. et al. 1993b.327 APPENDIX -------------------------------------------------------------------------------------------------------------------------------------. ENGINEERED MICROSTRUCTURES FOR NONLINEAR OPTICS -------------------------------------------------------. et al. et al..2.3 A New Type of Optical Bistability Mechanism: Nonlinear Case with One Incident Wave (Xu and Ming. 1997b.304 19.281 18.3 The Effective Nonlinear Optical Coefficients ---------------------------------------------------------------------------------.305 19.1 Bloch Wave Approach (Xu and Ming.288 18. 1996a.5 NONLINEAR OPTICAL FREQUENCY CONVERSION IN 1-D PERIODIC DSLS -------------------------------------------------------. 1997)----------------------------------------------------------------------------------------------------.315 19.2 Four-Path Switch: Linear Case (Feng and Ming.2 Preparation of DSL by Using Photorefractive Effect-------------------------------------------------------------------------. Qin.5.18.. et al.

There are four main phases in boron nitride. • and and N atoms. cubic-type BN (c-BN) is widely used. r-NB (b). Ishii. (from S. 1981). 1957). e. which is the second largest after diamond (Corrigan. Another prominent feature is its high thermal conductivity. Its elucidation is highly expected from the standpoint of nanostructure analysis.g. Neighboring sp2 sheets are weakly bound by van der Waals force. Boron and nitrogen atoms form hexagonal rings. 1952.1 Introduction Boron nitride (BN) is an important industrial material. since it does not react with iron. h-BN and rhombohedral-type BN (r-BN) are formed under ambient pressure (Pease.. w-BN (c) and (d). et al. respectively. Wentorf. 10. 6–9 W/(cm • deg). it is mainly used for grinding and cutting industrial ferrous materials instead of diamond. Nanomechanism of the Hexagonal-Cubic Phase Transition in Boron Nitride under High Pressure at High Temperature 10. which are linked by sp2 bonding and extend two-dimensionally in sheets. since nanophases are complicatedly involved during the transition.10. Because it is the second hardest material known to man (the hardest being diamond). respectively (Fig. The exact mechanism of the hexagonal-cubic transition is not clear.1 Projections of the crystal structure of h-BN (a). Their interplanar spacing is 0. It is then rather expensive.. Hexagonal-type BN (h-BN) is chemically stable at high temperature and therefore used as crucibles for single crystal growth. Since it is transparent without any color. 1963. c-BN is synthesized from h-BN under high pressure at high temperature (Bundy and Wentorf. Their stacking sequences are conventionally represented by ab′ and abc.334 nm for h-BN and r-BN.1(a) and (b)). respectively. Horiuchi) means B 1 . Figure 10. 1979).3328 nm and 0. it is used as a raw powder for a cosmetic material.

et al. 1993). et al.Wurtzite-type BN (w-BN) is prepared from h-BN under high pressure at room temperature (Bundy and Wentorf.1(c)).. The hexagonal-cubic transition is then prominently facilitated as compared to the non-milled case due to the mechanochemical effect.2 Processing Method to Get c-BN 2 .1(d)). It is found that the formation of w-BN plays an important role on the mechanism of the transition.. By using catalysts the pressure and/or temperature for the synthesis is considerably decreased (Endo. the initial h-BN powders are ball-milled so that w-BN includes many lattice defects. 1986). Their stacking sequence is represented by AB′ (Fig. For the structure of c-BN. but the products suffer from the contamination due to the catalysts. Wakatsuki.2087 nm) (Fig. 1979. Sei. 10.. 10. the stacking sequence is ABC (d111 = 0. In the present chapter. which is another high-pressure phase. 1963. The interplanar spacing becomes small (d0002 = 0. structural evolution during the hexagonal-cubic phase transition under high pressure at high temperature is examined in detail using high resolution transmission electron microscopy (HRTEM) and electron energy loss spectroscopy (EELS). 10. et al.2211 nm) since B and N atoms are linked by the sp3 bond and the sheets become puckered. In order to verify the validity of the proposed model.

1998). Besides. using a belt-type high-pressure machine (Akaishi. (+m): the signal of m-BN is obtained only in HRTEM images and ED patterns. w: wurtzite-type BN. hot-pressed material. m: monoclinic-type BN. Its formation under low pressure has been widely examined and the mechanism is under discussion at present. In the present study the starting material was h-BN hot-pressed in a cylinder shape. Transmission election microscopy (TEM) specimens were also prepared for these two cross sections by using a conventional method.c-BN is usually obtained by processing h-BN under high pressure at high temperature. Table 10.7 7. It was wrapped in Zr foil and pressed under high pressure (6. which was commercially obtained from Denkikagaku Co. it can be also synthesized at low pressure in a similar manner to diamond.7 Temperature (°C) — 1730 1700 1800 2000 2150 Time (min) — 30 30 20 20 20 Phases h h+c(+m) c+m+h+w c+m+h c+m c h: hexagonal-type BN. XRD analyses were carried out in both the longitudinal and transverse cross sections. as shown in Table 10.7 GPa) at high temperature (1700–2150°C) for 20–30 min.1 (He. The press direction was parallel to the cylinder axis. In order to clarify the effects of the press direction upon microstructure. et al.5 7. using Cu-Kα radiation.3 Characterization Method The recovered specimens were examined by X-ray diffraction (XRD). at room temperature. 1994). thin plates were cut out. 10.7 7. Sample 1 is a starting. (Type N-1). polished. et al. They were observed by a high-voltage electron microscope (model H-1500) at an accelerating voltage of 1000 kV with 3 .5–7. c: cubic-type BN. dimpled and ion-milled.7 7.1 Synthetic condition and products* Sample 1 2 3 4 5 6 * Pressure (GPa) — 6...

a resolving power of about 0. Arrowheads indicate the occurrence of small cracks. 10. as indicated by arrowheads in Fig.2 TEM image of the starting material of hot-pressed h-BN (sample 1).1 mm. Figure 10. 1994).4. the defocus spread of 10 nm.3 mrad.2. Horiuchi) 4 . They are closely packed in most regions. Their thickness fluctuates between 1 and 6 µm. and the beam convergence of 0. The software was developed by us (Horiuchi.4 Phase Transition of Boron Nitride 10. Plate-like crystals are closely packed.12 nm. h-BN Figure 10. It is noted that the grains have plate-like form. (from S. 10.1 Nanostructure of the Starting Material 1.2 is a typical structure of hot-pressed h-BN. Small cracks occur in some of the thick plates. A computer simulation of high-resolution transmission electron microscory (HRTEM) images was carried out by using the microscope parameters: the spherical aberration coefficient of 2. The electron energy-loss spectroscopy (EELS) analysis was carried out using an analytical electron microscope (model HF-2000) with a field emission gun at 200 kV.

t-BN Figure 10. 10. et al. 2.2 Phases and Nanostructures Appearing during the Hexagonal-Cubic Transition 5 . It is composed of 5 curved sp2 sheets and one dangling bond at the center. An arrowhead indicates the boundary between subplates. (from S. The small cracks observed in Fig. 1995).3 HRTEM image of h-BN with the incident electron beam along .4.3 also demonstrates that the dangling bonds usually arise at the edge of sp2 sheets. 10. Horiuchi) In some areas a semi-spiral structure is found at the edge of sp2 sheets (Fig. An inset schematically shows the formation of dangling bonds at the edge of the crystal. An example of a boundary between subplates is marked by an arrowhead. which is shown by an arrow.4).33–0. 10. taken with an incident electron beam parallel to of a h-BN plate.2 must have been formed at the boundary between subplates when the specimen was hot-pressed. The corresponding ED pattern is attached.3 is an HRTEM image with the corresponding electron diffraction (ED) pattern.. The formation of subplates must be a result of the weak chemical bond between the sp2 sheets. Most of the subplates are only several nm in thickness. it is identified to be a turbostratic-type BN (t-BN).Figure 10. It is found that plates are actually composed of "sub-plates".35 nm). The semi-spiral structure seems smaller in size compared to that found under high pressure (7. Figure 10. The situation is schematically depicted by an inset. From the morphology and the interplanar distance (d = 0. marked by an arrow.7 GPa) at high temperature (1800°C) (Horiuchi.

w-BN. (from S. Figures 10. w. and (f) from sample 6. The identified phases are listed in Table 10. (b) from sample 2. Horiuchi) Figure 10. Figure 10.10. Table 10. Figure 10. (a) is taken from sample 1 (cf.1.5(a)—(f) are from samples 1–6 indicated in Table 10. c-BN.4. c. m.5 and 10. (c) from sample 3.6 shows the XRD charts obtained from the longitudinal cross section of sample 1–3.5 XRD charts obtained from the transverse cross sections of samples 1–6. 10.6. Horiuchi) 6 .1). They were obtained from the transverse cross section. (from S. h-BN. (e) from sample 5.4 A semi-spiral structure of t-BN formed locally at the edge of a starting h-BN plate.1. (d) from sample 4. m-BN. h.1 XRD The results of XRD analysis are shown in Figs.2.

7 .

It is interesting to note that the initially intense h (0. Horiuchi) In sample 1. 10. This is due to the formation of m-BN (monoclinic-type BN.5(c) and 10.. 2n) peaks strongly decrease in intensity. 10.5(c).6(b) than in Fig. 2n) peaks are slightly higher in Fig.5(a). The residual h (0002) peak. becomes broad. It is noted that h (0. 1996). marked by a dark arrow.6(b)). most of h-BN still remains unchanged (Figs. Moreover. This means that the texture becomes more prominent in this sample. 10. h.5(b) than in Fig. 10. while the initially weak h ( ) and h ( ) peaks are still observable in Fig. 10. we note the appearance of w-BN in Fig. as shown by an open arrow.7 GPa at 1700°C (sample 3) a large amount of c-BN appears (Figs. (a) is taken from sample 1. the intensity ratio of h ( ) to h (0004) is different between Figs. while lower in Fig.6 XRD charts obtained from the longitudinal cross sections of samples 1–3. How the texture is formed will be discussed later. whose (0002) plane is normal to the press direction. 10. In sample 2. We can interpret this by the preferential formation of c-BN in the h-BN plates. 10. see below) (Horiuchi. 0. This means that there is a texture in the hot-pressed h-BN with a preferred distribution of (0002) normal to the hot-press direction.6(a). Under 7.5(a) and 10. 8 . h-BN.5(c). 10. et al.6(a).6(c)).Figure 10. (from S. 0.5(b) and 10. However. a very small amount of c-BN is formed. 0. 0. (b) from sample 2 and (c) from sample 3. 10. c-BN. c.

8 Geometry of h-BN plates before pressing (a) and after pressing (b). are folded under high pressure at high temperature.7 Characteristic structures formed in h-BN plates of sample 2. are slightly bent.At 1800°C (sample 4) the m (002) peak becomes slightly sharp (Fig. Arrowheads show the direction of pressure. 10. 10.5(d)). 10. while some others keep the plate-form with slight bending (Fig. Figure 10. (from S.8.7(a)). 10.6(a) and (b). whose plane was almost normal to the press direction initially. During folding and bending. Arrowheads indicate the direction of pressure. h-BN Figure 10. Some h-BN plates. Plates are frequently folded in (a) while bending in (b). The peak becomes very weak at 2000°C (sample 5. while some still remain nearly parallel to the press direction. Such structural evolution is schematically shown in Fig. Fig. 10. As stated above in relation to Fig.5(e)) and disappears at 2 150°C (sample 6. 10. These results clearly show that m-BN is an intermediate phase during the phase transition from h-BN to c-BN. Horiuchi) Figure 10. The plates are prominently folded locally (Fig.7 shows TEM images of the h-BN in sample 2.4. Frequent folding causes a zigzag shape. 10. (from S. 10. whose plate plane was parallel to the press direction initially.7(b)). most of the h-BN plates tend to be normal to the press direction. the plates.2. On the other hand. a strong texture has been developed in sample 2. Horiuchi) 9 .2 HRTEM 1. Fig.5(f)).

The lattice parameters of the monoclinic-type BN (m-BN) are α = 0. The optical diffraction patterns taken from small areas of 6. e.9. However. at the rightmost area of Fig. b = 0. 10. The folding of the initial h-BN plates mentioned above causes the shear. i. showing an enlarged region near the folding plane. 2. taken with the incident electron beam parallel to (He. The inset is the ED pattern taken from a region including the whole area of Fig. Figure 10. the symmetry changes from hexagonal to monoclinic. Recently its structure has been analyzed and clarified by HRTEM (Horiuchi. was detected in the course of the hexagonal-cubic transition (Corrigan and Bundy. 10.5(d).31–0. Corrigan. being in agreement with the result by XRD. et al.31 nm) than that for the normal h-BN mentioned above.33 nm. fits well to the real image.9 is an HRTEM image of sample 2. which shows a smaller interplanar distance (d = 0. An example of the XRD peak is shown in Fig..433 nm. et al.5 nm in size proves that the shear of the 0002 atom plane varies continuously in this region. As a result. 10. We may conclude that the formation of m-BN 10 .9. and weak spots indicated by arrowheads in the inset are from the conventional h-BN. 1998).9. inserted in Fig. 1975.5 nm × 6. Near the plane (0002) sheets are sheared with respect to each other and the interplanar distance is slightly decreased. It is clear that the major spots are from m-BN.. h-BN keeps the original symmetry. This means that h-BN still remains in this sample. c = 0. 10. A computer-simulated image for the h-BN. m-BN An X-ray diffraction peak of so-called "compressed h-BN". 1996).250 nm. as will be shown below.. β = 92°C—95°C. 1979). in the area slightly far from the plane.It has been found by HRTEM observation that the folding is achieved by a mechanical twinning. The contraction of the interplanar spacing occurs when the sp2 sheets are sheared to each other so that the symmetry changes from hexagonal to monoclinic. giving the value of β from 92°C (near the folding plane) to 90°C (slightly far from the plane).

10..has been initiated near the folding plane. together with the corresponding ED pattern. 10..10(a). The electron beam is incident parallel to the folding plane. Figure 10.5(b) and 10. The folding is due to the mechanical twinning. (from S. (b) Lattice relationship between h. Horiuchi) It can be seen also in the ED pattern of Fig. no clear XRD peaks of this phase have been obtained in Figs. in which a computer-simulated image is inserted. whose atomic arrangement is schematically depicted. 10. Since the volume of the m-BN is still very small. The lattice relationship between hand m-BN is schematically shown in Fig. Horiuchi) 11 . showing the details of the folding of h-BN plate in sample 2. 10.6(b). (from S. while h-BN is seen in the area at the right-hand side. et al. with the corresponding ED pattern. A typical HRTEM image of m-BN is shown in Fig. m-BN appears near with a corresponding ED pattern. Another inset in Fig. In samples 3 and 4.and m-BN. 10. in which the rotation angle is measured to be 66°C (He. The value of β approached what was previously reported (β is 92°—95°). 1997).9 that the two areas adjoining at the folding plane are . 1997).9 HRTEM image of sample 2. the shear of sp2 sheets became prominent and prevailed in larger areas.9 shows a schematic structure model of the twinning. in such an orientation relationship as the rotation of 57°C—71°C about the sheet normal We may then say that the folding was done by mechanical twinning.10(b) (Horiuchi. Figure 10. with the increase of the preparation temperature under 7.10 (a) HRTEM image of m-BN in sample 4.7 GPa. . et al. which has been taken from sample 4.

in a plate-like crystal. (from S. as is shown below (Fig. Figure 10.and c-BN phases. marked by an asterisk.11 HRTEM image of sample 4. since there is a distinct difference in the compressibility and in the thermal expansion between adjoining h. An ED pattern taken from the corresponding area is inserted. 10.12).Similar effect on the shrinkage of (0002) spacing can be expected from lattice bending. Plates of h-BN are sharply folded at the sites of arrows. A clear example for this is noted at the nucleation of c-BN. Horiuchi) 12 . showing a nucleation of c-BN.

in which the lattice fringes are prominently bent. (from S. The arrangement of bright spots in areas of downward arrows shows the monoclinic lattice distortion. 10. Horiuchi) 13 . An upward arrow in the c-BN grain shows the appearance of w-BN.11.12 HRTEM image of the boundary area between the c-BN grain and the surrounding h-BN matrix in Fig.Figure 10.

Some h-BN plates are folded. the lattice spacing between sp2 sheets is measured from 0.In the HRTEM observation of m-BN it was noted that this phase is stable for the long-time irradiation of the highly energetic electron beam. 3. The diffraction spots indicate the formation of c-BN. It should be noted that the w-BN is partially found in the grain as marked by an upward arrow. One of them is marked by an arrow.11. is from h-BN but it does not form a perfect circle. A small grain of c-BN is found and marked by an asterisk in a h-BN plate. compared to h-BN. The electron beam is incident almost parallel to of c-BN. This means that m-BN is formed. showing a nucleation stage of c-BN. This means that the chemical bonding in m-BN is substantially stronger than that in h-BN. Referring to the ED spots of c-BN.31 nm. From their arrangement it is noted that the sheets are slightly sheared along 14 . In the surrounding matrix the lattice planes of the sp2 sheet are prominently bending.11. 10. An inserted ED pattern corresponds to the image of Fig. marked by an arrowhead. c-BN Figure 10. The innermost diffraction ring. Nanoscale twins of c-BN with (111) boundaries are seen in the grain.34 to 0. From the ED pattern and HRTEM image the orientation relationship among c-BN.12 is an HRTEM image for the boundary area of the c-BN grain in Fig. w-BN and the surrounding h-BN matrix is known as follows. 10. Figure 10. In some areas bright spots are resolved.11 is a typical morphology of sample 4.

31–0. which are adjacent in the projection plane. A computer-simulated image for c-BN fits well to the real image.12 is measured as 0. The interplanar spacing of the bending lattice in Fig.e. respectively (Lynch and Drickamer. When temperature increases. and is another cause of the mutual lattice restraint. In this case the thin film for TEM observation was obtained by crushing the retrieved specimen. This shows the formation of m-BN. However. Here we have used the measured value (d111 = 0. 1989). i. the volume cannot be completely retrieved when the high pressure is removed because of mutual restraint at the boundaries. The distortion angle is different for different areas but lies in the range of 5°—9°.21 nm) of c-BN as a reference. This restraint must have caused the lattice bending observed above. It is clear that each twin slice contains only several atomic planes. 10. This will induce similar effect on the difference in the compressibility. Under the high pressure of 7. et al.. In the calculation the defocus amount is taken to be 80 nm underfocus.7 GPa. The corresponding ED pattern and a computer-simulated image of c-BN are inserted. 1974).13 shows an HRTEM image and the corresponding ED pattern taken from sample 5. Also. Slack and Bartram. Figure 10. 1952. We may then say that a bright spot appears at the center of a pair of B and N columns. the thermal expansion coefficient is significantly different between hand c-BN (Pease. the number of c-BN grains increases but the growth of the grains is not prominent for temperatures lower than 2000°C We have found that a large number of thin twins (nanoscale twins) have formed. (from S. showing the formation of nanoscale twins.and c-BN are compressed by about 89% and 98%. h.34 nm of d. Figure 10.the lattice plane. for the present case. Knittle. the array of spots is not rectangular but slightly distorted in the area marked by downward arrows. in which the two phases coexist. Horiuchi) 15 . 1996.13 HRTEM image of a c-BN grain in sample 5.. The diffraction streaks along 111 are just due to the shape effect of the nanotwins.

including secondary twins. (b) A corresponding ED pattern. Horiuchi) 16 .14(b) is the corresponding ED pattern. Figure 10. 4. Grains have grown to µm size and the thin twin plates have disappeared. the twinning along the second set of {111} planes appeared.14 (a) TEM image of a c-BN grain in sample 6. w-BN Figure 10.14(a) demonstrates a typical structure of the c-BN grain prepared at the highest temperature (sample 6). Instead. (from S.Figure 10.

A corresponding ED pattern is inserted.4.16 shows the EELS profiles in core-loss regions for h-BN (a). (from S.3 EELS Figure 10. although very locally in the latter sample. They face each other at the sites marked by circles. A corresponding ED pattern is inserted and verifies the orientation relationship of Eq.and w-BN in a grain. Typical. showing the coexistence of c-BN and w-BN. and those of w-BN by "w". c-BN (b) and m-BN (c). Figure 10. Figure 10.2. (10. and those of w-BN by "w".15 HRTEM image of sample 4.Small domains of w-BN are found in some c-BN grains of samples 3 and 4.15 is another example of HRTEM image taken from sample 4. showing the coexistence of c. narrow areas of c-BN are marked by "c". Typical. A fine electron beam of about 1 nm in diameter was used. They face each other at the sites marked by circles. narrow areas of c-BN are marked by "c". This is always the case for small grains of c-BN. 10. Leftward arrowheads show diffraction spots from c-BN.1). rightward ones those from w-BN. Horiuchi) 17 .

c-BN (b). Horiuchi) 18 . and m-BN (c).16 Core-loss EELS profiles from h-BN (a). (from S.Figure 10.

Seitz. efficient. 19 . In (b) there is only one main peak. they are usually self-contained. batteries are becoming a critical component (Ruetschi. photographic equipment. et al.1 General Overview of Batteries and Fuel Cells 11. 1999) and will continue to be used in a wide variety of consumer. σ* peak. convenient. As the technologies of electronics industry advance. For m-BN (c) there are also two peaks. π* and σ* peaks. However. giving freedom to utility power. respectively). 11.. In (a) there are two main peaks at 196 and 202.The condition of measurement was kept constant for all of them. reliable and can be easily configured to user requirements. Batteries have many advantages (Linden. respectively. Ondrey. lighting. Georgano. industrial and military applications in the 21st century. This difference implies that the band structure of sp2 sheets is different and the density of states for the π* bond becomes higher in m-BN than in h-BN. 1984) over other power sources. watches. 1991) for portable electronic devices. They are considered to correspond to the transition to π* and σ* bands. the π* peak is stronger than the σ* peak. 1996. 1995. 1997.5 eV (marked with π* and σ*. calculators.. as is the case of (a). memory backup and a wide variety of other applications. et al.1 Introduction Batteries and fuel cells are important power sources today (Berger.1.

the lead-acid battery. an electric current is induced to flow through the wires. As such.1 The gravimetric and volumetric energy densities of rechargeable lithium batteries as compared with those of other systems. equivalent to about 2–3 times more efficient than the combustion processes. hydrogen (Pohl. The most abundant element on the Earth. Figure 11. methanol. these are not limited by the Carnot efficiency of thermal engines and are usually 60% efficient. This huge consumption of fuel is responsible for the rapid depletion of our nonrenewable energy sources. 1950) subsequently constructed what was perhaps the first battery. On top of this.Beyond batteries. As these move through a strong magnetic field usually created by arrays of powerful magnets.or gas-fired power stations. fuel cells are able to promote energy diversity and provide a transition to renewable energy sources. There is a further loss of energy through transportation of the electrical supply by high voltage cables.2 An Overview of Batteries The first work on batteries was done by Volta (Applely and Foulkes. 1995) can be directly used in the functioning of fuel cells. ethanol and even diesel or gasoline fuel can be utilized. Ritter (Vinal. The introduction of the nickel metal hydride (NiMH) in the late eighties and the lithium ion (Li-ion) in the early nineties brought more energy to a given cell compared to the earlier generation of batteries including the nickel cadmium (NiCd) batteries. In 1859. Steam is then used to turn huge turbines and several rolls of wires are connected to these spinning turbines. At this end.1 compares the gravimetric and volumetric energy densities of rechargeable lithium batteries with those of other systems. these have lower emission levels. coal-fired stations are only around 30% efficient in the conversion of chemical energy from fuel to electrical energy. 1950) which later led to the development of the first practical rechargeable (secondary) battery.1. inefficient combustion of fuels usually creates disruptive impacts on the environment including pollution and strong possibility of global climate change. 1989) around 1800. including natural gas. Since this early work. 11. fuel cells are highly efficient and less pollutive power-generating systems that produce DC electricity through the combination of fuel and oxidant in an electrochemical reaction (Apple by and Foulkes. Alternative fuels containing hydrogen. 20 . because some available energy in coal is lost at every stage of conversion. Planté began the foremost studies (Vinal. the electrical supply homes is generated in coal. As a result. 1977). these are becoming more and more important. producing less CO2 associated with more traditional means of power generation. Chemical energy from coal is burnt to produce heat energy which changes water into steam. This has not been an efficient way of harvesting energy. Traditionally. Figure 11. a variety of new battery systems have been discovered and developed (McCroy. In fact. The electric supply is then connected to the power sockets by running cables throughout a large area. 1989). Because fuel cells convert chemical energy directly into electrical energy without the intermediate combustion processes.

an initial prototype Li-ion (AA size) cell made of carbon/lithium cobalt oxide (C/LiCoO2) was introduced to the battery world by Sony Energytec.1. 1984) of a battery cell during charge and discharge is shown schematically in Fig. Any leakage of electrons from the anode to the cathode within the cell reduces the current generated by the battery. the United States and Europe engaging in Li-ion research by mid-1994.2 The operation of a battery cell during (a) charge and (b) discharge. a joint venture company A & T Battery. 21 . the oxidation takes place. Carbon/lithium manganese oxide (C/LiMn2 O4) technology was later developed in 1992 by Bell Communications Research. was formed by Asahi Chemical Industry and Toshiba Battery to manufacture C/LiCoO2 cells. 11. Thus. The electrical circuit is completed in the electrolyte by the flow of negativeions (anions) and positive ions (cations) to the anode and cathode. When a piece of zinc metal is assumed as the anode material and chlorine (Cl2) is the cathode material. with most manufacturers of small rechargeable batteries in Japan.In 1990. electrons will flow from anode through an external load once the cell is connected to it.2. it was clear that lithium ion rechargeable had became the most promising battery technology. At the anode. respectively.1) take place.1 Operation Principle of Batteries The operation (Linden. the discharge reactions (shown in Table 11. Subsequently. while at the cathode a reduction reaction occurs. During discharge.2. Figure 11. the electronic current delivered by the cell is matched by the ionic current within the cell. Basically. 11.

such batteries are characterized by high energy density. However. Primary cells are not capable of being easily recharged and are suitable for one-time use only. they are usually light. only to deliver energy to the load upon demand. 11.(ZnCl2) Batteries are the lifeblood of many low-power portable devices which face an increasing demand. flat discharge curves and good low-temperature performance. Secondary batteries can be electrically recharged to their original condition after discharge by passing current through them in the opposite direction to that of the discharge current.→ ClZn + Cl2 → Zn2+ + 2Cl. Essentially. they can be identified as primary (non-rechargeable) or secondary (rechargeable) cells. inexpensive. They are also more environmentally friendly as there is less concern for battery disposal compared to primary batteries. The secondary batteries are used essentially to lower cost since they can be used multiple times. of high energy density and possess good shelf-life. high discharge rates. They are good storage devices for electrical energy and are often charged by a primary energy source.Table 11. they can be classified into two broad categories. In addition to their ability to be recharged.2 Research of High Energy Storage Batteries 22 . Depending on the batteries' capability of being electrically rechargeable.1 Reaction mechanisms for a Zn/Cl2 cell Zn/Cl2 Cell Anode (negative electrode) Cathode (positive electrode) Overall Zn → Zn2+ + 2eCl2 + 2e.2.1.

1994). Presently. namely the nickel metal hydride (NiMH). * Li+ = lithium Ion. 23 . Figure 11. the United States and western part of Europe by the year 2000. and lithium ion (Li Ion). Shown in Fig. SLA=sealed lead acid. three advanced rechargeable battery technologies appeared in the market as well. rechargeable alkaline manganese (RAM). United States and Western Europe to the year 2000. NiMH = nickel metal hydride. RAM = rechargeable alkaline manganese. In recent years. NiCd = nickel Cadmium. 11.3 The market scenarios for the penetration of rechargeable cells in Japan. nickel cadmium (NiCd) batteries held more than 80% of world markets while sealed lead-acid (SLA) batteries held about 13% (Seitz and Shimosato.3 are the market share for the penetration of rechargeable cells in Japan. the huge spate of research into rechargeable lithium batteries has led to the emergence of lithium-solid positive-electrode prototype cells ever since the first Li/MoS2 production cell. where it was basically dominated by two rechargeable battery technologies.In the early world market for small rechargeable batteries.

4. The basic design of a fuel cell is illustrated in Fig. a Welsh judge and scientist. silent reactions produce an electric current. is supplied from one surface of the electrode. Migration of the hydrogen ions occurs through the electrolyte to the catalytic surface of the oxygen electrode (cathode). The formation of water due to combination of the hydrogen ions. the reactions occur via a chemical mediator known as the electrolyte.11. oxygen and electrons on the cathode's catalytic surface.1. In fuel cells run on hydrogen.4 Schematic operation principle of a fuel cell with a solid polymer electrolyte.3 An Overview of Fuel Cells The first fuel cell (O'Sullivan. hydrogen. Two catalyzed carbon electrodes are immersed in an electrolyte while the fuel.4. the following events occur: 1. 3. 2. 11. Movement of the electrons through the external circuit to the catalytic surface of the oxygen electrode. 1972) was built up by Sir William Grove.1 Operation Principles of Fuel Cells Fuel cells have beneficial operating characteristics unmatched by any other technology. the use of fuel cells had been confined to laboratories until recent decades.1. oxygen from the air reacts with the input hydrogen in such a way that a voltage is generated between the two electrodes. 24 .3. When the electrodes are electrically connected through an external load. As in batteries. Unlike batteries. However. It was only in the 1960s that fuel cells were engaged to provide power on board for the Gemini and Apollo space missions (Kordesch and Simader. fuel cells can be continuously recharged. 11. however. forming hydrogen ions and electrons. Dissociation of hydrogen occurs on the catalytic surface of the anode. in 1839. Figure 11. 1996) while providing the astronauts with clean drinking water.

the ionic species carrying charge from one electrode to another varies and they are generally distinguished by the type of electrolytes used. The fuel cell depicted in Fig.→ 2H2O + 2eO2 + 4e.4 has an acidic electrolyte (such as phosphoric acid or a proton-exchange membrane).ions (alkaline fuel cells) or CO2-3 ions (molten-carbonate fuel cells). OH.ions (solid oxide ceramic fuel cells). rather than remote fuel cells can also be utilized for portability. 11. Commercialization has been a leading theme for fuel cell technology in recent years.2. With the additional advantage of on-site operation. In various other fuel cells.2 Reaction mechanism for fuel cells Acidic electrolyte Anode Cathode Overall Alkaline electrolyte H2 + 2OH. The major use of fuel cells as potential replacements for internal combustion 25 . relying on H+ ions to carry charge from the anode to the cathode. Table 11.1.→ 2H2O 2H2 + O2 → 2H2O 11. For example. the charge can move from cathode to anode via O2. the reaction mechanisms for a hydrogen fuel cell in acidic and alkaline electrolytes are shown in Table 11.+ 2H2O → 2OH2H2 + O2 → 2H2O H2 → 2H+ + 2eO2 + 4H+ + 4e.2 Research of Fuel Cells Fuel cells were first considered for applications where noxious emissions or noise would be objectable and where water was unavailable.3.For different types of fuel cells.

the world's largest fleet of fuel cells. In a pursuit for "clean" power. Ballard Power Systems of Vancouver. The electrolytes used must possess high ionic conductivities and low concentration gradients as the choice of materials used is greatly limited by the effective rates of reactions on the catalytic electrodes. the application of nanomaterials is essential to the development of practical fuel cells. The current state of fuel cells today revolves around the use of electrocatalysts (Sandstede. 1988) is being actively promoted. For example.1. Small platinum (Pt) particles of sizes 2–3 nm at monolayer coverage offer the high surface areas needed for improved catalytic activity. the Gemini space flight missions. but capable of passing four times the current at the same operating voltages.S. buses and other vehicles. 1990. the solid polymer electrolyte fuel cell system (Kordesch and Simader. Besides huge investments into the research of fuel cells by the U. determine and mould the material requirements for batteries. low interest loans and grants to support early purchases and drive down costs. which determines both their operating temperature and the materials they can employ. similar to the earlier Nafion membrane (Gavach and Pourcelly. Fuel cells also require porous electrodes showing a microscopic three-dimensional interface between the reactant gas and electrolyte phases. several vehicle demonstration projects have already been employed around the world.. fuel cells may start to appear as alternatives to internal combustion engines in automobiles. and Germany are promoting fuel cell developments with tax credits. Ballard made a subsequent breakthrough in fuel cell performance through a new sulfonated fluorocarbon polymer membrane from Dow Chemical. 1996) of the General Electric Company was used. Thus. British Columbia. 1996) into the lattice structure. it is thus realized that the application of nanophase structures is desirable as this would provide the large surface areas required for chemical reactions to occur. which implies that a huge surface area can be electronically accessed. 11. In 1987. Various factors have contributed to the growth of new battery technologies. it is also the intention of 26 . Canada. These factors.engines in transportation (Lemons. In the first major practical use of fuel cells. and Daimler-Benz of Germany. et al. such as the performance requirements and specific environmental constraints of hand-held products will. Fuel cells are characterized by the electrolytes used (Appleby. New Jersey. Besides the use of nanomaterials in fuel cells. including those of H Power of Belleville.S. the U. The microstructure of the oxide film is composed of a network of interpenetrating pores. Nanosized metallic powders are often used for this purpose. Srinivasan. 1989) required for the charge transfer reactions which produces the flow of electricity. Japan.4 Importance of Nanomaterials in Batteries and Fuel Cells There are many chemical and physical requirements (Julien and Nazri. 1992) developed by DuPont. Early in the next century. Department of energy (DOE). 1995). 1990. This is mandatory for applications in electric vehicles since only nanosized Pt powders can offer the high electrocatalytic activity of the charge transfer reactions while keeping the catalyst loadings low. 1996). Prater. 1972. 1994) which will limit the choice of materials in the application of batteries and fuel cells. in turn. The key feature of the application of nanostructured materials in the development of batteries (Graetzel. To increase the energy density in batteries. Simultaneously. Government owns and operates 30 fuel cell cogeneration units. improvements in battery performance have been achieved by the use of nanocrystalline oxide films for the anode material. Appleby and Foulkes. particular by for rechargeable lithium ion batteries is the ease of rapid intercalation of Li+ ions (Dutta.

10.5.5 Mechanism of Hexagonal-Cubic Transition 10.1 Model for the Transition Mechanism The fact that w-BN domains are always included in small c-BN grains suggests that the phase transition from h-BN to c-BN occurs not directly but through w-BN. • and mean B and N atoms. When w-BN converts to c-BN. a rotation of the lower part of the unit by 60° is apparently necessary. The sequence of the atomic Shockley-type partial dislocation occurs.this chapter to cover in detail the use of nanomaterials in secondary batteries rather than their primary counterparts.. Figure 10. The rotation requires the breakdown of chemical bonds. Figure 10. i. Horiuchi) 27 . (d) In order to decrease mechanical strain. (c) If the similar stacking faults successively occur at every second sheet. (from S.17(a) shows structure units of w. 1989). the resultant structure will be that of c-BN. (a) Shows conversion from structure unit of w. to that of the c-BN locally.(reight) to that of c-BN (left). At the tip of the stacking fault a is the Burgers vector. nano-scale twins are introduced. From these experimental results we may say that h-BN changes initially to w-BN and then to c-BN. whereas together with c-BN is also obtained at high temperature (Sekine. (b) The rotation is achieved by introducing a stacking fault in w-BN at the plane marked by a triangle.and c-BN.17 A model for the mechanism of the conversion from w-to c-BN. stacking changes from AB′ AB′ A′ to AB′ C′ A′ C′. On giving shock compression to h-BN only w-BN has been obtained at medium temperature. respectively.e. It seems difficult and may be one of the main reasons why c-BN forms only under high pressure at high temperature. On the conversion a rotation of the lower part of the units by 60° is apparently necessary.

Chemical bonds are broken down at the end of the stacking fault. to that of the c-BN locally. The dislocation is taken to be of edge type. (b) On the movement of the dislocation in the rightward direction the chemical bonds at the positions of the arrow 2 are cut..17(a). When the dislocation moves. (a) shows atomic positions on the planes marked by a triangle in Fig. while those of arrow 1 28 . At the tip of the stacking fault a Shockley-type partial dislocation appears and the atomic array at the dislocation core is severely disturbed.A possible mechanism for the rotation may be as follows: first we introduce a stacking fault at the plane in w-BN.e. The real movement of atoms at the dislocation core will be discussed later (Fig. 10. 10.18 Atomic movement during the conversion from w-to c-BN. i.. 10.17(b). Figure 10. i.e. This means that the atoms have rearranged to achieve the rotation of Fig. On the formation of the stacking fault the sequence of the atomic stacking changes from AB′ AB′ A′ to AB′ C′ A′ C′. marked by a triangle in Fig.17(b). the area of c-BN extends. along the dislocation line.18). which runs along the vertical arrow 1. 10.

A twin contains four sheets.17(d). (10.13). 1993).12 and 10. a large mechanical strain is induced because of large deformation in shape. 10. 29 . In the successive stage of the dislocation motion the chemical bonds of arrow 3 are cut and those of the arrow 2 are restored. the resultant structure will be c-BN (Fig. An example of a twin structure is shown in Fig. (from S. 10. depending on how frequently the stacking faults are introduced. The model proposed above can explain the orientation relationship among h-. however. In principle. This supports the validity of the model.are restored. 10.17(c)). It is important to note that twins can relax the mechanical strain induced on the transition to c-BN. In this case. w. This is the reason why many nanoscale twins have occurred in c-BN (Figs.and c-BN of Eq.1). Other combinations of stacking faults cause twinning (Pirouz and Yang. The relaxation could be more effective if they would contain fewer sheets. Horiuchi) If similar stacking faults successively occur at every second sheets. twinning is possible with any thickness.

such stacking sequences can be observed at the parts indicated by arrowheads in w-BN of (a). w-BN has appeared in h-BN matrix. in which w-BN has just been initiated in an h-BN matrix under high pressure at high temperature (Horiuchi. In the successive stages of the dislocation motion the chemical bonds of arrow 3 are cut and those of arrow 2 are restored.5. It should be noted that the movement of atoms is simple and almost along the same direction as that of the Burgers vector of the dislocation. Figure 10.3 Facilitation of Synthesis of c-BN by Mechanochemical Effect An essentially important factor in the transition mechanism proposed above is an introduction of lattice defect like dislocations as well as related stacking faults in w-BN. The rate-controlling stage in the atomic rearrangement must be the breakdown of chemical bonds.18 shows atomic positions on the planes marked by a triangle in Fig. which runs along the vertical arrow 1. the atomic rearrangement is also simple to form the stacking faults. In h-BN a Frank-type edge dislocation is seen at the part of an arrow. Chemical bonds are broken down at the end of the stacking fault. 10. as shown in Fig.e.2 Atomic Movement during the Conversion from w-to c-BN Figure 10. When the partial dislocation is of pure screw-type.19(a) shows an HRTEM image of the specimen. That is. 10. since the chemical reaction in a solid substance is accelerated under the introduction of mechanical strain. h-and w-BN coexist with an interface nearly parallel to (0002). which was ball-milled and heated at 1350°C under 7. et al. (from S.. an anti-phase boundary is formed.7 GPa. 1998). Horiuchi) 30 . a prominent mechanochemical effect is observed. In fact.10.17(b). The stacking sequence is ab′ c′ bc′ bc′ a′. Since the dislocation is not brought in w-BN.7 GPa at 1250°C for pre-milled specimens and 1450°C for non-milled ones. 10. Figure 10. although each unit in the resultant structure has apparently been "rotated". In this series of experiments the formation of c-BN has started on the treatment under 7..19 (a) HRTEM image of the specimen. we have tried to do ball-milling on the initial h-BN powders under the expectation that the obtained w-BN include more defects. Unidirectional movements of atoms are necessary to achieve the apparent "rotation" also in this case. while those of arrow 1 are restored. On the movement of the dislocation in the rightward direction the chemical bonds at the positions of arrow 2 are cut. i. along the dislocation line.5. In order to verify this from the standpoint of actual experiments.17(b). (b) schematic representation of (a). In w-BN a similar stacking fault is included so that a stacking sequence of AB′ AB′ C′ BC′ B is created.

31 .

mentioned above. 1998). In fact. 10. where the Frank-type dislocations are densely formed. et al. as shown in Fig. 10.19(a). a region with a stacking sequence AB′ AB′ C′ A′ B′ A occurs.19(b) is a schematic representation of (a). In w-BN a similar stacking fault is included so that a stacking sequence of AB′ AB′ C′ BC′ B is created. which was prepared at 1350°C under 7. their density was locally counted to be 2 × 1012 cm-2 after treating the ball-milled h-BN under 7. however. In n-BN a Frank-type edge dislocation is seen at the part indicated by an arrow. Some of them are paired to form loops. an anti-phase boundary is formed. Since the partial dislocation of Shockley type is required to move only a short distance in this case.20 HRTEM image of the specimen. as mentioned above in relatio to Fig. 10. For example.Figure 10. arising from the Frank-type dislocations. In fact. Horiuchi) 32 .20 (Horiuchi. introducing a stacking fault. This type of reaction.and w-BN coexist with an interface nearly parallel to (0002).17(b). if some small areas with such a stacking sequence as above.7 GPa after milling the starting h-BN. h. Figure 10. Since the dislocation is not brought in w-BN. This means that a thin region of c-BN is nucleated. We may then say that the formation of the Frank-type dislocation in high density is the essential reason for the occurrence of the present mechanochemical reaction. There are many dislocations with the Burgers vector (c/2) [0001]. thin areas of c-BN will be formed. This may be possible in the area.. many Frank-type dislocations have been created during ball-milling together with Shockley type ones.7 GPa at 1350°C. It should be pointed out that. according to HRTEM observation. The stacking sequence is described as ab′ c′ bc′ bc′ a′. as indicated by arrowheads. The stacking sequence for c-BN partly occurs. The former increased the number under high pressure at high temperature. A possible source of the partial dislocation may be the anti-phase boundary. the reaction becomes more probable. If a Shockley-type partial dislocation moves. are tentatively formed and adjoin to each other. such stacking sequences can often be observed at the parts indicated by arrowheads in w-BN of Fig. requires the movement of dislocations for long distance. (from S.

The geometry in Fig.. It is reasonable to consider that h-BN grains in such orientation suffered from severer deformation than those in other orientations so that the mechanochemical effect is more prominent. the transition to c-BN preferentially occurred in h-BN.and w-BN. which formed locally in the milled specimen. whose (0002) plane is initially normal to the press direction. 10. it was noted that h-BN first nucleates in the amorphous BN. 1999). crystallize to h-BN. the introduction of lattice defects is effective on facilitating the hexagonal-cubic transition. The interface is however slightly tilted against the common (0001) plane of h.and w-BN. It must be useful to release the lattice direction in the (0002) plane of h. This must be a useful method to synthesize c-BN in an industrial scale.We may assume that the Frank-type dislocations have been created when the amorphous areas. In fact. misfit of about 2% along the Finally. which has been formed by a stronger ball-milling (Huang. 10.19 shows that the w-BN has been created by a simple compression of h-BN in the 0001 direction. 33 . et al. The tilting is accomplished by the presence of dislocations in h-BN.6 Prospect As mentioned.

the symmetry changes from hexagonal to monoclinic (Fig.7(a)). 10. According to HRTEM.12).12 and 10. This is due to the formation of m-BN.13) and their growth is not prominent as long as the temperature is lower than 2000°C. a very small amount of c-BN is formed in h-BN in the recovered sample 2 (Figs.31–0.5 GPa at 1730°C. The residual h(0002) peak becomes broad.250 nm.5–7. most of the h-BN plates tend to be normal to the press direction so that the texture becomes strong (Fig.14). 10. During folding and bending. suggesting that their band structures of sp2 sheets are different (Fig. 10. b is 0. 10. As a result. 3. 10. There is a definite orientation relationship among c-BN. Besides. Nanoscale twins with (111) boundaries are seen in the c-BN grain (Fig. 7.5(d)). t-BN with curved sp2 sheets was locally found (Fig. 5. 10. Each plate is actually composed of "sub-plates" with thickness of several nano-meters (Fig. 10. Structural evolution in BN during the hexagonal-cubic phase transition without any catalysts is examined using XRD. Moreover.5GPa at 1730 °C.7 GPa at 1700°C (sample 3) a large amount of c-BN appears (Figs. Grains have plate-like form with a thickness between 1–6 µm (Fig. Under 7.7 GPa) at high temperature(1700–2150°C). 10. As heating temperature increases.2). They occur in h-BN plates (Fig. 10. Besides. 10. 10.3).5(f)).433 nm..15). a substantial amount of w-BN appears. Grains of c-BN appear under 6. 6. 9. There is such a texture as the preferred distribution of 0001 normal to the hot-press direction. 10.1).1). 10. the plates of h-BN are prominently folded locally in sample 2 (Fig. The plate plane is parallel to (0001). 10. At 1800°C (sample 4) the m(002) peak becomes slightly sharp (Fig. c is 0. w-BN and surrounding h-BN. The peak becomes very weak at 2000°C (sample 5. using a belt-type high-pressure machine (Table 10. In the model it starts with the conversion from h. 10. being in agreement with the previous result of shock compression to h-BN (Sekine. 1999). The folding of the initial h-BN plates causes the shear (Fig.5(c) and 10.6(c)). 10.10).9). 10.33 nm. A model for the mechanism of the hexagonal-cubic transition was proposed (Fig. small areas of w-BN are partially found in the grain. Besides. β is 92°—95°. Fig.and m-BN the π* peak is weaker than the σ* peak for h-BN. the texture of h-BN becomes more prominent. We may then consider that the phase transition from h-BN to c-BN occurs not directly but through w-BN. The lattice parameters of m-BN are: a is 0. The "rotation" can be 34 . The starting material was h-BN hot-pressed in a cylinder shape. 1990). 10.16). The folding was performed mainly by mechanical twinning.6(b)). 10.11).4). Small domains of w-BN are always found in small grains of c-BN (Figs.How much it is facilitated may depend on the degree of the mechanical strain introduced. 2. They are consisted of nano-twins (Fig. but stronger for m-BN.5(b) and 10. It was pressed under high pressure (6. The most severe point of the transition is in the second conversion.17). In the EELS core-loss patterns of h. 4.7 Conclusions 1. In order to prove this we have performed a much stronger BM (planetary-type BM) and a more prominent mechanochemical effect was observed. According to XRD (Table 10. which was obtained commercially. which was pressed under 6. At 2150°C grains have grown with the formation of secondary twins (Fig. 8.to w-BN and is completed by that from w. The details will be published elsewhere (Huang. HRTEM and EELS. showing that m-BN is an intermediate phase during the phase transition from h-BN to c-BN. in which a rotation of atom groups is apparently necessary.5(e)) and disappears at 2150°C (sample 6. 10. 10. the number of c-BN grains increases. et al. 11.to c-BN.8). Fig.

J. J. Yamaoka. Akaishi. G. 14. Fukunaga. Drickamer.. 1999 Ishii T. 78.. pp. and R. Phys. D. Appl. Phil. R. Lett. 10.Resolution Transmission Electron Microscopy.. 1883 (1994) Bundy F. Horiuchi. W. Wentorf. Jpn. The resultant w-BN included a number of dislocations (Fig. 10. 4241 (1997) Horiuchi S. J. 1. Wentzcovitch. Sato. 10. He. and M. Jr. Y. and T. References Akaishi M. 82. eds... and M.20) exercises a positively effect so that the distance required for the movement of Shockley type dislocations is shortened. L. T.. T. T. Taniguchi. 13.19) and the formation of c-BN was prominently facilitated as compared to the non-milled case due to the mechanochemical effect. When the dislocation moves. 994 (1979) Corrigan F. the formation of the Frank-type dislocation in high density (Fig. L. Chem. 12. Mater. Sato. M. J.to c-BN can be explained by a simple atomic rearrangement based on the movement of dislocation (Fig. Y.. Bundy. H.. Taniguchi. T. and F. Akaishi. Y. L. Horiuchi.. L. In order to verify the validity of the above model from the standpoint of actual experiments. Mao. The atomic movement during the conversion from w. Sci. 337. Phys. Phys. L1612 (1995) Horiuchi S. J. the initial h-BN powders were ball-milled and many dislocations and related stacking faults were introduced. Barber. 182 (1996) Horiuchi S. 44. Phys.. Lett.achieved by introducing a stacking fault in w-BN. the local area of c-BN extends.. 38. 34. Cryst. Fundamentals of High. 52. Plenum Press. 63. 243 (1998) He L. and M. and M. 181 (1996) Pease R. Iwata. 3812 (1975) Endo T. Iwata.. and M. He. F... Sato. Surf. L. S. and S. 211 (1994) Horiuchi S. and H.18).12 and 10. J. Y. L. J. Growth. to be published. Mater. J. Amsterdam. L. Microsc. 197 (1997) Horiuchi S. R. Tech. 349 (1989) Lynch R. Taniguchi. Taniguchi T. Akaishi. Anal. Taniguchi and S. J.. P. S. In: 6th AIRAPT Conf. Akaishi. 68. L. Acta Crystallog. 40. 1676 (1979) He L. 356 (1952) 35 . 10. R.. M. Sci. Mag. 285 (1981) Knittle E.13). Jeanloz. and M. Onoda. 3. Appl. M. in order to release a mechanical strain a number of nanoscale twins are formed in c-BN (Figs. J.. pp. He. Huang. L. He. North-Holland. Phys. and S. and S. Appl. New York. P. R. At the tip of the stacking fault a Shockley-type partial dislocation locates. Chem. High Pressure Science and Technology. J. 12. Nature. Huang. T. M. 5. Moreover... Cohen. T... by Timmenhaus K. vol.. O. 1065 (1998) Huang J. Sekikawa and M. L. 1144 (1963) Corrigan F. Horiuchi. Res. L. J. Phys. Ishii. Chem.

Elsevier Sci. the catalytic metal nanoparticles are typically obtained on high surface area support materials such as Al2 O3 and SiO2. and S.1 Chemical Vapor Deposition Chemical vapor deposition of hydrocarbons over metal catalysts has been a classical method to produce various forms of carbon fibers. Chem. 89 (1974) Wakatsuki M. Ultramicrosc. Jr. 1988. W. 36 . H. Endo. The base-growth mode involves the metal catalyst particle pinned on the support substrate. 1994). Baker and Rodriguez. 46. J. and S. as well as the type of hydrocarbon feedstock and growth conditions.. et al. 256 (1986) Wentorf. 511 Slack G. by Schmidt S. C. J. The typical growth temperature Tg is typically 500 °C ≤ Tg ≤ 1000 °C. B... 1989. eds.. R. pp. 189 (1993) Sei H. Shock Compression of Condensed Matter-1989. Bartram. 1984). Subsequent precipitation of carbon from the supersaturated catalyst particle will then occur and lead to the formation of a carbon tube structure (Fig. and L.2. Takano. and J. Akaishi. Multi-walled or single-walled can be synthesized by CVD depending on the particle size.2 Synthetic Strategies for Various Nanotube Architectures 13. and the nanotube lengthens with a particle-free closed end. A. The first step in a CVD process involves the absorption and decomposition of hydrocarbon molecules on transition-metal (Fe. Snyder.1. and G. Typically. filaments and multi-walled nanotubes in the past (Tibbetts. F. Single-walled nanotubes are shown as examples. 1160 (1993) Sekine T. etc.Pirouz P.) catalytic particles.. 139–140. J. 1983. et al.. Pub. Co. Davison. Carbon feedstock is supplied from the base where the nanotube interfaces with the catalyst material (Fig. 51. 1987. Physica. 13.. right panel). K. 956 (1957) 13. Right panel: tip-growth mode. Tibbetts. Phys. left panel). W. Tibbetts. Phys. 26. 1990. 13. Figure 13. The tip-growth model involves a metal catalyst particle at a nanotube end being carried away as the nanotube lengthens (Fig. two modes of nanotube growth can operate in CVD. Fujita.. B. The carbon atoms diffuse into the interior of the catalyst to form a metal-carbon solid state solution (Baker. M. The size of the catalytic particles determines the size of the nanotubes. 2. 1989.V. J. Yamaoka. Left panel: base-growth mode. Appl.1).1.1 Schematic growth modes of carbon nanotubes in CVD. 13. Diamond Related Mater. Ni. Johnson. Yang. The carried-along particle is responsible for supplying carbon feedstock needed for the nanotube growth. For the synthesis of nanotubes. N..

previous methods have relied on growth of nanotubes in confined environments including the pores of mesoporous silica or channels of alumina membranes (Li. 1996).2 Growth of Self-oriented Multi-walled Nanotubes In controlling the orientation of nanotubes during CVD growth. We have found that nanotubes can self-assemble into aligned structures during CVD growth. 1998. CVD growth using the substrate is then carried out in a 2 in.. Che. a pitfall of CVD synthetic approaches has been that defective tubular carbon materials tend to be formed. Only recently. The nanotube towers exhibit very sharp edges and corners with no nanotubes branching away from the blocks. Our synthesis approach involves catalyst patterning and rational design of the substrate to enhance catalyst-substrate interactions and control the catalyst particle size. and the driving force for self-alignment is the van der Waals interactions between nanotubes (Fan. et al. et al. 1998b).. 13. et al. Kyotani..2(a) shows a scanning electron microscope (SEM) image of regularly spaced arrays of nanotube towers grown on top of patterned iron squares on a porous silicon substrate. 13. 1998. et al. 1992). Pan.. Figure 13. 1998a. The resulting substrate consists of a thin nanoporous layer (pore size 3 nm) on top of a macroporous layer (with submicron pores) (Vial and Derrien.Notably.. The high resolution SEM image (Fig. 13.2. et al. we have developed a CVD approach to grow nearly perfect SWNTs by using methane as the carbon feedstock (Kong. This result will be presented later in the chapter. 1996. Patterned catalyst squares on the porous silicon substrate are obtained by evaporating a 5 nm thick iron film through a shadow mask. 1994. et al. inset) within each block are well aligned along the direction perpendicular to the substrate surface. The length of the nanotubes and thus the height of the 37 . tube furnace at 700°C under an ethylene flow of 1000 sccm/min for 15–60 min.. 1999). The substrates are porous silicon obtained by electrochemical etching of n-type silicon wafers in HF/methanol solutions.2(b). Smith and Collins.2(b)) reveals that the MWNTs (Fig.

and the width of the towers is controlled by the size of the openings in the shallow mask. 1983. The porous silicon substrates exhibit important advantages over plain silicon substrates in the synthesis of self-aligned nanotubes. Endo. Growth on substrates containing both porous silicon and plain silicon portions find that nanotubes grow at a higher rate (in length/min) on porous silicon than on plain silicon.. 1994. 1989). 1999). filaments and MWNTs (Tibbetts. During CVD growth. CVD synthesis of high quality SWNTs is only recent. The smallest self-oriented nanotube towers synthesized by our method are 2 µm × 2 µm wide. Figure 13. et al. which allows the growth of nanotubes perpendicular to the substrate. Since the nanoporous layer on the porous silicon substrate serves as an excellent catalyst support. The mechanism of nanotube self-orientation involves the nanotube base-growth mode (Fan. This result suggests that ethylene molecules can permeate through the macroporous silicon layer and thus efficiently feed the growth of inner and outer nanotubes within the towers.2 (a) Scanning electron microscopy image of arrays of bundled multi-Walled nanotube towers. the outmost walls of nanotubes interact with their neighbors via van der Waals forces to form a rigid bundle. (b) A high resolution SEM showing aligned MWNTs within a tower. The inset shows a TEM image of the bundled MWNTs. Baker and Rodriguez. Structurally perfect SWNTs can now be grown in a CVD process using methane as carbon feedstock and iron-oxide nanoparticles supported on high surface 38 .. 1990. Snyder. 13. et al.3 Enable the Growth of Single-Walled Nanotubes by CVD Chemical vapor deposition methods have been very successful in synthesizing carbon fibers. 1988.2. and the strong catalyst-support interactions prevent the catalyst particles from sintering at elevated temperatures during CVD growth. the iron catalyst nanoparticles formed on the nanoporous layer interact strongly with the substrate and remain pinned on the surface. The nanotubes grown on porous silicon substrates exhibit monodispersed diameters since catalyst nanoparticles with a narrow size distribution can be formed on the porous supporting surface.towers can be controlled in the range of 10–240 µm by varying the CVD reaction time. However.

Catalytic decomposition of methane by the transition-metal catalyst particles is thus the dominant process in SWNT growth (Kong. We have found that methane is stable at elevated growth temperatures without appreciable self-pyrolysis. we have found that a good catalyst material for SWNT synthesis necessarily exhibits strong metal-support interactions. Within the methane CVD approach. 1998a). et al.. 13. et al.7–5 nm with a peak at 1. and obtain nearly defect-free tube structures. The strong metal-support interactions allow high metal dispersion and thus a high density of catalytic sites. our optimized catalyst consists of Fe/Mo bimetallic species supported on a sol-gel derived alumina-silica multicomponent material (Cassell... Bulk quantities of high quality SWNTs can be synthesized by optimizing the catalyst. and retains these characteristics at high temperatures without sintering. we find that the chemical and textural properties of the catalyst materials dictate the yield and quality of SWNTs (Cassell. The open pore structure of a catalyst allows efficient diffusion of reactant and intermediate hydrocarbon species. 39 . High temperature conditions (850–1000°C) are employed in the growth in order to overcome high strain energies in forming small diameter SWNTs (<5 nm). 1999b). 1999b). et al. Thus far. We believe that the rate-limiting step in SWNT CVD growth involves gas diffusion. The image illustrates remarkable abundance of individual and bundled SWNTs that are free of defects and amorphous carbon coating. Shown in Fig. This is based on the results that high SWNT yielding catalysts exhibit large pore volumes in the mesopore regime (Cassell. et al. 1998a. et al. 1999b). Figure 13..3 A TEM image of SWNTs synthesized in bulk using a catalyst supported on a sol-gel derived alumina-silica hybrid material. Weight gain studies find that the yield of nanotubes can be as high as 45 wt%. possesses a high surface area and large pore volume.7 nm. The diameters of the SWNTs are dispersed in the range of 0.area alumina as the catalyst (Kong. et al.. Inset: an example of the frequently observed SWNT ends that are closed and free of metal particles. 1999b). Through systematic studies. This stability prevents the formation of amorphous carbon that tends to cause catalyst poisoning and overcoating the nanotubes.3 is a transmission electron microscopy (TEM) image of SWNTs synthesized in bulk by using this catalyst.. 1998b. The choice of methane is critical to the CVD approach to SWNTs. Cassell.

Baker. On the other hand. et al. 1998b.3 inset). left panel) (Tibbetts. 1990. the tip-growth mode operates when the metal-support interaction is weak.. et al. Kong. 1989.2. 1984. et al. In the methane CVD method. 1987. Careful high resolution TEM imaging of the SWNTs synthesized by our CVD method frequently observes closed tube ends that are free of attached or encapsulated metal particles (Fig. Cassell. Amelinckx.. These observations suggest that SWNTs grow in the methane CVD process predominantly via the base-growth process (Fig. Tibbetts.1. In contrast. The opposite ends are typically found embedded in the catalyst support particles when imaged along the lengths of the nanotubes. This is rationalized by the increased catalytic sites and the facilitated base-mode growth processes. 1998a.13. 1983. 1999b). 13. 1989. Tibbetts. we find that enhancing metal-support interactions leads to significant improvement to the performance of the catalyst material in producing high yield SWNTs... 13. et al.4 Growth Mechanism of SWNT The states of nanotube ends contain rich information about nanotube growth mechanisms. Base-growth operates when strong metal-support interactions exist so that the metal species remain pinned on the support surface. catalysts with 40 . 1994.

et al. Some of the nanotubes have one end attached to a catalyst island and the other end terminated between islands. As described in a later section. Atomic force microscopy (AFM) images of SWNTs on a nanotube-chip are shown in Fig. which is consistent with TEM results obtained with bulk SWNT materials. The diameters of the nanotubes are measured to be in the range of 0. 13. Thus. By using substrates patterned with 1–5 µm wide catalytic islands.7–4. Figure 13. 13. Further understanding of the chemistry of catalysts and nanotube growth will undoubtedly lead to the synthesis of bulk quantities of high quality SWNTs approaching the kilogram scale.0 nm. 1998b. et al. 1999. Nanotubes bridging islands with both ends attached to the opposing islands are also observed..5 Growth of Isolated Single-Walled Nanotubes on Controlled Surface Sites The successful CVD synthesis of SWNTs in bulk forms has led to a straightforward synthetic route to addressable individual nanotube wires.2. 1999b). where the synthesized nanotubes extending from the catalyst islands are clearly observed. the bridging SWNTs allow reliable electrical connections to be made from the macroscopic scale to individual SWNTs.. et al.4 (a) An AFM image of SWNTs grown from patterned catalyst islands on a silicon oxide substrate. Soh.. we obtain "nanotube chips" that contain isolated single-walled nanotubes grown from desired locations on the substrates (Kong. 41 .weak metal-support interactions lead to aggregation of metal species and reduced nanotube yield and purity (Cassell. 1999). (b) Image of an individual SWNT bridging adjacent islands.4. our controlled chemical synthesis opens up a new route to individual nanowire electrical circuits that are needed for fundamental and practical purposes.

42 .

1998b). In an area containing towers in a square configuration. Figure 13.004 g). 1991) of a flat PDMS stamp inked with a film of the precursor material. Ferguson..5(b)).5 (a) SEM image of a suspended SWNT "power-line-like" structure. 43 . We have devised a synthetic strategy that leads to suspended SWNTs directed towards controlled orientations parallel to the plane of a silicon substrate. 13. FeCl3 · 6H2O (0. The SWNTs are suspended bridges grown from catalyst material placed on top of regularly patterned silicon tower structures. Directed free-standing SWNT networks are formed by nanotubes growing to adjacent towers and suspended above the surface. (b) SEM image of a square of suspended SWNT bridges.5(c)..6 Growth of Suspended SWNTs with Directed Orientations Obtaining single-walled carbon nanotube architectures with nanotubes in aligned orientations has been challenging. we observe that highly directional suspended SWNTs are formed on the synthesized sample.5(c). where suspended tubes forming a power-line-like structure can be seen. a square of suspended nanotube bridges is obtained (Fig. 13. 13. (c) TEM image of a SWNT bridge suspended between silicon towers. 1998. AlCl3 · 6H2O (2.5(a).0 g) (Yang. we selectively place the precursor on top of tower arrays pre-made on a silicon substrate (Cassell.13. we show a TEM image of a suspended SWNT bridge between silicon towers.. and an image (Fig. Inset: a high magnification TEM image showing the structure of a SWNT.4 g). Well-aligned SWNT bridges are obtained in an area of the substrate containing isolated rows of towers as shown in Fig.. 1998a. The directions of the suspended tubes are determined by the pattern of the towers.09 g) and MoO2Cl2 (0. nanotubes emanate from the top of the towers. 1999a). Directionality of the suspended tubes is simply a result of the rationally designed substrate. Subsequent CVD growth using the substrate yields SWNTs emanating from the towers. whereas nanotubes directed towards other orientations fall onto the sidewalls of the towers (not easily resolved under SEM). et al. et al. 13. A specific precursor material consists of ethanol (40 mL) and 2-butanol (20 mL) solutions of P-123 block copolymer (1. et al. The nanotubes growing towards adjacent towers become suspended. During the CVD growth. inset) showing the high resolution structure of the SWNT. When examining with an SEM. Calcination at 700°C for 4 h leads to the formation of alumina/silica mixed oxides confined on the tower tops.2. In Fig. Using contact printing (Xia and Whitesides. The synthesis approach begins with developing a series of liquid-phase catalyst precursor materials that allow for uniform film formation and large-scale catalyst patterning.

44 .

The method should open a new window in characterization and device applications of organized nanowire architectures in suspended states or after being transferred onto flat substrates.The directed growth of suspended SWNTs presented here involves developing a new type of liquid phase catalyst material. contact printing of catalyst onto designed substrates and CVD synthesis. 45 .

Seitz.1. Planté began the foremost studies 46 . et al. calculators. Steam is then used to turn huge turbines and several rolls of wires are connected to these spinning turbines. inefficient combustion of fuels usually creates disruptive impacts on the environment including pollution and strong possibility of global climate change.. 1991) for portable electronic devices. they are usually self-contained. Georgano. fuel cells are highly efficient and less pollutive power-generating systems that produce DC electricity through the combination of fuel and oxidant in an electrochemical reaction (Apple by and Foulkes.1 General Overview of Batteries and Fuel Cells 11. At this end. There is a further loss of energy through transportation of the electrical supply by high voltage cables. 1989).1. photographic equipment. Traditionally. As such. On top of this.1 Introduction Batteries and fuel cells are important power sources today (Berger.or gas-fired power stations. As a result. the electrical supply homes is generated in coal. 1989) around 1800. fuel cells are able to promote energy diversity and provide a transition to renewable energy sources. memory backup and a wide variety of other applications. Nanomaterials for Energy Storage: Batteries and Fuel Cells 11. these have lower emission levels. Beyond batteries.. Batteries have many advantages (Linden. Chemical energy from coal is burnt to produce heat energy which changes water into steam. 1995) can be directly used in the functioning of fuel cells. Because fuel cells convert chemical energy directly into electrical energy without the intermediate combustion processes. 1997. convenient. hydrogen (Pohl. As these move through a strong magnetic field usually created by arrays of powerful magnets. industrial and military applications in the 21st century. 1984) over other power sources. equivalent to about 2–3 times more efficient than the combustion processes. coal-fired stations are only around 30% efficient in the conversion of chemical energy from fuel to electrical energy. Ondrey. The most abundant element on the Earth. producing less CO2 associated with more traditional means of power generation. lighting. et al. 11. these are not limited by the Carnot efficiency of thermal engines and are usually 60% efficient. ethanol and even diesel or gasoline fuel can be utilized.11. 1995. This has not been an efficient way of harvesting energy. giving freedom to utility power. Alternative fuels containing hydrogen. because some available energy in coal is lost at every stage of conversion. batteries are becoming a critical component (Ruetschi. 1950) subsequently constructed what was perhaps the first battery. an electric current is induced to flow through the wires. reliable and can be easily configured to user requirements. In fact. including natural gas. efficient.2 An Overview of Batteries The first work on batteries was done by Volta (Applely and Foulkes. In 1859. methanol. Ritter (Vinal. 1999) and will continue to be used in a wide variety of consumer. 1996. watches. This huge consumption of fuel is responsible for the rapid depletion of our nonrenewable energy sources. As the technologies of electronics industry advance. these are becoming more and more important. The electric supply is then connected to the power sockets by running cables throughout a large area.

1 compares the gravimetric and volumetric energy densities of rechargeable lithium batteries with those of other systems. the lead-acid battery. the United States and Europe engaging in Li-ion research by mid-1994. Figure 11.1 The gravimetric and volumetric energy densities of rechargeable lithium batteries as compared with those of other systems. Carbon/lithium manganese oxide (C/LiMn2 O4) technology was later developed in 1992 by Bell Communications Research. was formed by Asahi Chemical Industry and Toshiba Battery to manufacture C/LiCoO2 cells. a variety of new battery systems have been discovered and developed (McCroy. Basically. electrons will flow from anode through an external load once the cell is connected to it. 11. respectively.(Vinal. At the anode. 1950) which later led to the development of the first practical rechargeable (secondary) battery. a joint venture company A & T Battery. During discharge.2. while at the cathode a reduction reaction occurs.1. an initial prototype Li-ion (AA size) cell made of carbon/lithium cobalt oxide (C/LiCoO2) was introduced to the battery world by Sony Energytec. with most manufacturers of small rechargeable batteries in Japan. it was clear that lithium ion rechargeable had became the most promising battery technology. Thus. the oxidation takes place. 11. the electronic current delivered by the cell is matched by the ionic current within the cell. 1984) of a battery cell during charge and discharge is shown schematically in Fig. Since this early work.2.1 Operation Principle of Batteries The operation (Linden. Figure 11. 1977). In 1990. Any leakage of electrons from the anode to the cathode within the cell reduces the 47 . Subsequently. The electrical circuit is completed in the electrolyte by the flow of negativeions (anions) and positive ions (cations) to the anode and cathode. The introduction of the nickel metal hydride (NiMH) in the late eighties and the lithium ion (Li-ion) in the early nineties brought more energy to a given cell compared to the earlier generation of batteries including the nickel cadmium (NiCd) batteries.

However. Depending on the batteries' capability of being electrically rechargeable.1 Reaction mechanisms for a Zn/Cl2 cell Zn/Cl2 Cell Anode (negative electrode) Cathode (positive electrode) Overall Zn → Zn2+ + 2eCl2 + 2e. they are usually light. only to deliver energy to the load upon demand. the discharge reactions (shown in Table 11. of high energy density and possess good shelf-life. When a piece of zinc metal is assumed as the anode material and chlorine (Cl2) is the cathode material. They are good storage devices for electrical energy and are often charged by a primary energy source. such batteries are characterized by high energy density. The secondary batteries are 48 . they can be classified into two broad categories. Secondary batteries can be electrically recharged to their original condition after discharge by passing current through them in the opposite direction to that of the discharge current.(ZnCl2) Batteries are the lifeblood of many low-power portable devices which face an increasing demand. high discharge rates. In addition to their ability to be recharged. Figure 11. Essentially.current generated by the battery.→ ClZn + Cl2 → Zn2+ + 2Cl. Table 11. flat discharge curves and good low-temperature performance.2 The operation of a battery cell during (a) charge and (b) discharge. Primary cells are not capable of being easily recharged and are suitable for one-time use only. inexpensive. they can be identified as primary (non-rechargeable) or secondary (rechargeable) cells.1) take place.

11. 1994). and lithium ion (Li Ion). namely the nickel metal hydride (NiMH). * Li+ = lithium Ion. RAM = rechargeable alkaline manganese. 11.2. the huge spate of research into rechargeable lithium batteries has led to the emergence of lithium-solid positive-electrode prototype cells ever since the first Li/MoS2 production cell. rechargeable alkaline manganese (RAM). SLA=sealed lead acid.3 The market scenarios for the penetration of rechargeable cells in Japan. the United States and western part of Europe by the year 2000. Shown in Fig. United States and Western Europe to the year 2000.3 are the market share for the penetration of rechargeable cells in Japan. Presently. 49 . nickel cadmium (NiCd) batteries held more than 80% of world markets while sealed lead-acid (SLA) batteries held about 13% (Seitz and Shimosato. They are also more environmentally friendly as there is less concern for battery disposal compared to primary batteries. NiCd = nickel Cadmium. Figure 11. In recent years. three advanced rechargeable battery technologies appeared in the market as well.used essentially to lower cost since they can be used multiple times.1. NiMH = nickel metal hydride. where it was basically dominated by two rechargeable battery technologies.2 Research of High Energy Storage Batteries In the early world market for small rechargeable batteries.

the use of fuel cells had been confined to laboratories until recent decades. However. 11. It was only in the 1960s that fuel cells were engaged to provide power on board for the Gemini and Apollo space missions (Kordesch and Simader.1. Unlike batteries. in 1839. fuel cells can be continuously 50 . 1972) was built up by Sir William Grove. silent reactions produce an electric current.1 Operation Principles of Fuel Cells Fuel cells have beneficial operating characteristics unmatched by any other technology.3.11. 1996) while providing the astronauts with clean drinking water. As in batteries.3 An Overview of Fuel Cells The first fuel cell (O'Sullivan. however. a Welsh judge and scientist.1.

11.4. OH. In fuel cells run on hydrogen. the reactions occur via a chemical mediator known as the electrolyte. For example. Figure 11. Movement of the electrons through the external circuit to the catalytic surface of the oxygen electrode. oxygen from the air reacts with the input hydrogen in such a way that a voltage is generated between the two electrodes. When the electrodes are electrically connected through an external load. the reaction mechanisms for a hydrogen fuel cell in acidic and alkaline electrolytes are shown in Table 11. 4. Migration of the hydrogen ions occurs through the electrolyte to the catalytic surface of the oxygen electrode (cathode). the charge can move from cathode to anode via O2. the following events occur: 1. The basic design of a fuel cell is illustrated in Fig.ions (alkaline fuel cells) or CO2-3 ions (molten-carbonate fuel cells). relying on H+ ions to carry charge from the anode to the cathode. is supplied from one surface of the electrode.2.recharged.2 Reaction mechanism for fuel cells 51 . The fuel cell depicted in Fig. 11. 3. For different types of fuel cells. In various other fuel cells. Dissociation of hydrogen occurs on the catalytic surface of the anode. The formation of water due to combination of the hydrogen ions.4 Schematic operation principle of a fuel cell with a solid polymer electrolyte. 2.4 has an acidic electrolyte (such as phosphoric acid or a proton-exchange membrane). hydrogen. the ionic species carrying charge from one electrode to another varies and they are generally distinguished by the type of electrolytes used. forming hydrogen ions and electrons. Two catalyzed carbon electrodes are immersed in an electrolyte while the fuel. Table 11. oxygen and electrons on the cathode's catalytic surface.ions (solid oxide ceramic fuel cells).

Government owns and operates 30 fuel cell cogeneration units. particular by for rechargeable lithium ion batteries is the ease of rapid intercalation of Li+ ions (Dutta. the U. Srinivasan. Besides huge investments into the research of fuel cells by the U. Japan. To increase the energy density in batteries. fuel cells may start to appear as alternatives to internal combustion engines in automobiles. which implies that a huge surface area can be electronically accessed. In the first major practical use of fuel cells.2 Research of Fuel Cells Fuel cells were first considered for applications where noxious emissions or noise would be objectable and where water was unavailable. et al. low interest loans and grants to support early purchases and drive down costs. buses and other vehicles. Various factors have contributed to the growth of new battery technologies. similar to the earlier Nafion membrane (Gavach and Pourcelly.→ 2H2O + 2eO2 + 4e. New Jersey. Early in the next century.4 Importance of Nanomaterials in Batteries and Fuel Cells There are many chemical and physical requirements (Julien and Nazri. Ballard Power Systems of Vancouver. Simultaneously. 1994) which will limit the choice of materials in the application of batteries and fuel cells. determine and mould the material requirements for batteries..1. 1990. 1992) developed by DuPont. rather than remote fuel cells can also be utilized for portability. but capable of passing four times the current at the same operating voltages.1.+ 2H2O → 2OH2H2 + O2 → 2H2O H2 → 2H+ + 2eO2 + 4H+ + 4e. and Daimler-Benz of Germany. The major use of fuel cells as potential replacements for internal combustion engines in transportation (Lemons. The key feature of the application of nanostructured materials in the development of batteries (Graetzel. In 1987. Commercialization has been a leading theme for fuel cell technology in recent years. the Gemini space flight missions. 1996). In a pursuit for "clean" power. 1996) of the General Electric Company was used. such as the performance requirements and specific environmental constraints of hand-held products will. 1996) into the lattice structure. including those of H Power of Belleville. British Columbia. 1988) is being actively promoted. Canada. Department of energy (DOE). Ballard made a subsequent breakthrough in fuel cell performance through a new sulfonated fluorocarbon polymer membrane from Dow Chemical. Prater. For example. 1990. in turn. and Germany are promoting fuel cell developments with tax credits. it is thus realized that the application of 52 . improvements in battery performance have been achieved by the use of nanocrystalline oxide films for the anode material. the solid polymer electrolyte fuel cell system (Kordesch and Simader. With the additional advantage of on-site operation.S. several vehicle demonstration projects have already been employed around the world. the world's largest fleet of fuel cells. These factors.S. The microstructure of the oxide film is composed of a network of interpenetrating pores.Acidic electrolyte Anode Cathode Overall Alkaline electrolyte H2 + 2OH. 11.→ 2H2O 2H2 + O2 → 2H2O 11.3.

. et al. commonly used in high energy density applications. being the lightest of all metals. The electrolytes used must possess high ionic conductivities and low concentration gradients as the choice of materials used is greatly limited by the effective rates of reactions on the catalytic electrodes. nickel metal hydride (NiMH). attempts to develop rechargeable lithium batteries failed and research has since shifted to a non-metallic lithium battery. 1980. Lewis in 1912. 1985). Appleby and Foulkes.1 Classifications of Advanced Batteries Today. Nanosized metallic powders are often used for this purpose.2. Due to this inherent instability. 11. lithium ion polymer (Li-ion-P). 53 .1. The temperature would approach the melting temperature of metallic lithium which could result in violent explosions (Wilkinson. 1972. all being of the rechargeable type.nanophase structures is desirable as this would provide the large surface areas required for chemical reactions to occur. The current state of fuel cells today revolves around the use of electrocatalysts (Sandstede. has the greatest electrochemical potential and provides the largest energy content. is the fastest growing technology. Scrosati. but it was not until the seventies that the first non-rechargeable lithium batteries became commercially available.. 1990). 1995). The pioneering work for research on lithium batteries was started by G. Fuel cells are characterized by the electrolytes used (Appleby.2 Batteries and Nanomaterials 11.1 Lithium Ion (Li+-Ion) Battery The lithium ion battery system (Pistoia. Fuel cells also require porous electrodes showing a microscopic three-dimensional interface between the reactant gas and electrolyte phases. Thus. it was found that occasional shorts from lithium dendrites developed in lithium electrodes could cause thermal runaway. especially during the charging process. This is mandatory for applications in electric vehicles since only nanosized Pt powders can offer the high electrocatalytic activity of the charge transfer reactions while keeping the catalyst loadings low. Small platinum (Pt) particles of sizes 2–3 nm at monolayer coverage offer the high surface areas needed for improved catalytic activity. N. and nickel cadmium (NiCd) batteries. Despite the fact that it is the latest to emerge from the laboratory into the real-world applications. the most promising batteries are based on the lithium ion (Li-ion). which determines both their operating temperature and the materials they can employ. it is also the intention of this chapter to cover in detail the use of nanomaterials in secondary batteries rather than their primary counterparts. 11.2. 1989) required for the charge transfer reactions which produces the flow of electricity. However. this revolution in battery technology is targeted to fulfil the requirements for future applications like electric vehicles and biomedical devices such as an artificial heart (Owens. 1994. the application of nanomaterials is essential to the development of practical fuel cells. 1984). et al. Besides the use of nanomaterials in fuel cells. 1995). Lithium (Bach. The concept of shuttling lithium ions between insertion electrodes was first proposed in the 1980s (Lazzari and Scrosati.

54 .Armand. Mizushima. the cathode is an electronically conducting host into which the Li+ ions are inserted from the electrolyte as guest species and charge-compensated by electrons from the external circuit. removal of electrons from the cathode by an external field will facilitate the flow of Li+ ions back to the electrolyte and hence restores the parent host structure. et al. 11.. chemicals such as lithium cobalt dioxide (LiCoO2) were used. composing of a carbon anode. On charge.. the anode can be elemental lithium itself (Yang. 1980. The addition of electrons to the anode by the external field attracts charge-compensating Li+ ions back into the anode to restore it to the original composition. the Sony cell was based on this "rocking chair" concept. 1984) between the two electrodes (the "rocking chair" technology). 1980. which is at least twice that of NiCd batteries. et al. An example of the lithium insertion process is illustrated in Fig. A lithium-insertion compound is usually used for the electrodes whereby there is a host matrix into/from which the guest species Li+ can be inserted or extracted reversibly without any change in the arrangement of the host atoms. 1997).. 1996). For example. Li+-ion batteries avoid the potential flammability and dendrite-shorting problems (Brown. LiCoO2 cathode and a non-aqueous electrolyte. The lithium ion is much safer and has a reasonably high energy density. 1985). Such a concept has been demonstrated with the layered TiS2 cathode which consists of a close-packed hexagonal sulfide ion array. Tarascon. In principle. it is found necessary to use a reductant host for lithium.5 An example of the lithium insertion process with the layered TiS2 cathode consisting of a close-packed hexagonal sulfide ion array. On the other hand. The new graphite electrode that has emerged provides a relatively flatter discharge voltage curve than the coke electrode and is capable of delivering a higher current while remaining cool during both the discharge and charge processes. In the present market. namely the coke version provided by Sony and the graphite version that has been adapted by most other manufacturers.5. The chemical reactions at the anode and cathode of a lithium secondary battery must be reversible. 1988) characteristic of metallic lithium rechargeable batteries by having lithium ions shuttle back and forth (Venkatasetty. The anode supplies Li+ ions to the Li+ ion electrolyte while directing electrons to the load circuit upon discharge. in practice. albeit that they yielded a lower energy density compared to lithium metal (Buchmann. there are two basic types of Li+-ion batteries. Auborn and Barbario. As a result. et al. 1987. Figure 11.

The overall reaction is When the NiMH battery was first introduced. safety and cost.11. 1999). the Li-polymer battery will offer a high energy density with low self-discharge but may only be suitable for low-power applications. there was great publicity about its "memory-free" status.1. Such a design avoids the presence of any leakage and high flammability of the liquid electrolyte used in Li-ion and lithium batteries. the Li-polymer battery system is a rechargeable yet potentially cheaper version of the Li-ion battery (Birke. However. the Li-polymer will provide more than thrice the energy density compared to NiCd batteries. today research has shown that they suffer the same "memory" effects (Davolio and Soragui. When commercially available.3 Nickel Metal Hydride (NiMH) Battery The nickel metal battery cell consists of a positive nickel hydroxide electrode and a negative electrode comprising hydrogen-absorbing alloys put in an alkaline electrolyte. since it was believed that the NiMH battery need not be fully discharged before each charging cycle. 11. ruggedness. If fully developed.2. The projected commercial market is expected to commence by the year 2000.1. et al.2 Lithium Ion Polymer (Li-ion-P) Battery Closest to commercial viability is lithium polymer technology. which seeks to improve the advances made by liquid electrolyte Li-ion batteries in recent years. 55 . 1998. The original concept of the Li-polymer battery was based on the use of a solid polymer electrolyte which offers great potential in design flexibility with respect to fabrication.2. Currently under development..

11. it is the most demanding on exercise requirements to prevent any "cyclic memory" effects.2 Major Components of Batteries Batteries have had such a long history that major developments have led to more diversified applications. and cost are important factors. video cameras. Traditionally. these incremental improvements in higher capacity over nickel cadmium batteries are often at the expense of reduced cycle life and lower load current. 1996. however. an amalgam. Electrodes in batteries can be broadly categorized into four groups with respect to their mode of operation. 1997). However. the sharp edges of these crystals may pierce the separator and cause a high self-discharge or an electrical short. An electrode is a condensed phase which has the property of electronic conduction: it can be a semi-conductor or a metallic conductor taking on various forms. or a solid metal. The crystals should remain small. Nevertheless. there are still some basic components common to the structure of every battery: the electrodes and the electrolyte. The NiCd battery possesses the shortest charge time. A battery consists of a group of interconnected electrochemical cells. Nevertheless. 1996) Besides. Electrodes are in direct contact with the electrolyte which is an ionic conductor and can be a solid or an aqueous phase. The problem now is not so much on the "memory" effects but on the effects of crystalline formation. In the modern NiCd battery technology. 1996) in much the same way as nickel cadmium (NiCd) batteries. When "memory effects" occur. et al. e.1. 1998). The crystalline formation which causes capacity loss is created by the nickel plate. Under certain circumstances. NiMH batteries are commonly used in cellular phones. delivers the highest load current and offers the lowest cost-per-cycle. a liquid... which may take a number of differing forms (Barak. Required in applications where long life. cell capacity will be limited by the positive electrode as the generated oxygen at this electrode has to be recombined.4 Nickel Cadmium (NiCd) Battery The nickel cadmium battery is one of the most mature and well-understood technologies today. 1980).2. this problem was virtually solved with the advancements in battery technology and hence the elimination of this phenomenon. Another form of memory that occurs on some cells is the formation of an intermetallic compound consisting of nickel and cadmium which holds some of the needed cadmium and imposes an extra resistance in the cell (Davolio and Soragni. particularly so nowadays with more rudimentary use of new materials. a metal common to both the NiMH and NiCd chemistries (Thaller and Zimmerman. video cameras and laptop computers where high energy is of utmost importance. high discharge rates. g. many oxides and even sulfides. the active materials are present in finely divided crystals (Buchmann. 56 . and power tools. This is achieved by the application of an excess negative material in the ratio of 3 : 2 with respect to the positive electrode. NiCd batteries found lasting uses in portable radios. graphite or carbon conducting carbides. Sato.Buchmann. hence obtaining maximum surface area but this is not the case.2. borides or nitrides. 11. the crystals actually grow up to 150 times the original size and drastically reduce the surface area (Buchmann. 1997).

3. small-particle electrode is necessary as shown in Fig. the utilization of a large area of electrode material in the electrochemical reactions. Figure 11. (c) wet-proofing agent. 4. the metal does not play any other role in participating in the reactions. the construction of a porous. lithium ion mobility and rate capability can be increased by keeping the particle size small. 2.6. A metal electrode or alloy in contact with an electrolyte containing the same ions of the metal. i. Electrochemical performances are strongly influenced by the powder characteristics such as particle size. some additional difficulties arising from the need to recycle the systems have been reviewed elsewhere (Sequeira and Hooper. As such.e. For example. Typically. An inert metal electrode at which an oxidation or reduction may take place with electron transfer. For the more popular secondary batteries.6 The construction of a porous.1. More recently. An inert conductor in contact with a salt or oxide and totally in contact with an electrolyte containing an ion which undergoes an oxidation or reduction with electron transfer. small-particle electrode in the electrochemical reaction involving the ionic transport across an interface: (a) gas. Other than acting as a source or sink of electrons. By convention. 1994) have been as solid electrolytes which are ionic conductors at their operating temperature. These include relatively low diffusion coefficients for ionic transport within the intercalation materials and the various failure mechanisms. which is also an ionic conductor. 11. a liquid such as water or other solvents. Where the electrochemical reaction involves a gas phase across an interface. A metal in contact with its salt or oxide form which stays in contact with an electrolyte containing the anion of the salt or hydroxyl ions. 1985). porosity. The achievement and retention of a relatively high electrode capacity. the electrolyte contains dissolved salts. 57 . this is represented by M Mn+(sol).. provides the medium for the transfer of charges as ions inside the cell between the anode and cathode. requires good electronic contact between particles over several charge/discharge cycles. (d) electrolyte. The electrolyte. surface area and morphology of the electrode properties. (b) carbon particle. certain crystalline and amorphous substances (Julien and Nazri. acids or alkalis to impart the required conductivity. the metal is oxidized and may dissolve freely to provide electron flow as in Zn/air primary batteries.

U. This is critical in establishing cost effectiveness. (Reisner. S.. the traditional material used for batteries usually has more than 50% pores. is composed of a layered oxide with Ni3+ ions residing on every basal plane of the octahedral sites in a close-packed cubic array of oxide ions (Zimmerman.2. et al. et al. 1994). nanostructured β-nickel hydroxide has been synthesized. as with most batteries. S. the present cathodic material has a much higher 58 . et al. trivalent nickel hydroxide is reduced to divalent nickel hydroxide under the consumption of water. et al.. Inc. Lee. 1996). 1998).1 Nickel Cadmium/Nickel Metal Hydride Electrodes The cathode for the nickel cadmium or nickel metal hydride battery. and the grains having an average particle size of 5 nm. initiated several wet chemical synthesis approaches for these active nanostructured battery materials (Reisner. 1999).2. and this hexagonal form of Ni(OH)2 can significantly boost the energy density of the nickel cadmium/nickel metal hydride or even nickel zinc batteries. To solve these problems. Nanocorp.. 1997) for use in a variety of energy storage applications such as batteries.1 Electrodes 11. the opposite reactions take place. the loss of conductivity associated with it (Reisner. 2–5 nm in diameter by 15–50 nm long. For over 90 years. 1997) can be compensated by the addition of nanophase cobalt particles. under the conditions of superplasticity in nanophase hard ceramics and intermetallic materials.3. Self-discharge is often caused by the decomposition of NiOOH. Nanocorp. Inc. lower levels of Co are utilized while.. on the other hand. On discharge. several mechanisms such as self-discharging (Ikoma. et al.3. With the nanosized particles capitalizing on the huge surface area. Due to its costly nature. the possible degradation of the separator and migration of cobalt from the positive electrode. On charge. 1996) and loss of conductivity can cause capacity loss in the NiMH system upon long term storage. 1984.. In this way. it was proposed that the capacity recovery of the battery can be improved by the addition of stable conductive powders such as Ni 210 (Singh. et al. high energy densities close to the theoretical densities are attainable even at ambient temperatures. of which there were a significant number of large pores not required for electrochemical efficiency. For instance.1. 1986). The protons provide a network of hydrogen bonding between the O—Ni—O sandwich layers with one hydrogen bond per oxygen atom in Ni(OH)2 (Yamada.. However. the protons may be reversibly inserted into the hydrogen-bonding network of NiOOH if charge compensation can occur via the introduction of electrons into the Ni3+/Ni2+ couple as indicated by the reaction below: Cobalt metal or oxides at 5–10 wt% are usually deposited on the Ni(OH)2 cathodes to impart conductivity (Ferrando and Lee. which are typical of nanopowders. while the metallic cadmium is oxidized to cadmium hydroxide.3 Applications of Nanomaterials in Advanced Batteries 11. The assynthesized β-Ni(OH)2 powder is a mixture of highly nanoporous fibers and equiaxed grain particles with fibers being ca. the main reasons being that Ni 210 powders possess very fine morphologies and high surface areas. Thus. after recognizing that the metallic oxide Ni(OH)2 can also show similar behavior.2. NiOOH. Several unique nanostructured materials have been developed by U. Clearly.11.

a metal oxide intercalation compound as the positive electrode and a non-aqueous liquid or solid polymer electrolyte. hence creating various defects both on the surface and the interior of the powder particles.. 1997) is one such example. It was also found that mixed-valent transition metal oxides tend to be good electronic conductors. which was usually carbon-based.2 Lithium Rechargeable Electrodes The earliest rechargeable lithium battery design consisted of a negative electrode fashioned from lithium metal. 1995.1. Kao. In their study. which supplies the Ni regions surrounding the ZrCrNi alloy particles. In addition. and with few exceptions they are generally stable against disproportionation reactions. et al.. Bruce. Favorably. Where both the anode and the cathode are hosts for the reversible insertion or removal of the working ion into/from the electrolyte.. 1992. the use of conducting additives such as Co particles is necessary to improve the activities as cathodes. et al.. the electrochemical cell is commonly called a "rocking chair". 1991) with a hollandite structure exhibiting an unusual "bird's nest" morphology (Feng.. 1998) to modify the electrocatalytic activity and activation behavior of the ZrCrNi alloy. Besides. After much research. AB2. 59 . commercially available lithium ion batteries are made with the more expensive LiCoO2 cathodes (Huang. Each "bird's nest" is about 10 µm in diameter. This geometry has potential applications as an intercalation material in lithium ion rechargeable batteries as well as in zinc/manganese dioxide rechargeable alkaline cells... 1994. Numata. the active materials would be able to attain a homogeneous porosity with a narrow pore distribution. et al. 1994). electrochemically activated nanocrystalline ZrCrNi powder particles were also formed after the milling process. It was reported that the Ni nanoparticles not only serve as electrocatalytic reaction sites but as hydrogen adsorption sites as well. LiMn2O4 or LiCoO2. 1998). Nanofibrous MnO2 (Kordesch and Weissenbacher. Capable of boosting the performance of both the nickel alkaline and lithium rechargeable batteries in a cost-effective manner. Rossouw. γ-MnO2 (Davidson. less toxic and can be prepared by easier methods than can the cobalt oxides.3. or a swing battery (Julien and Nazri. 1998. 1996. 1999) have been studied more extensively as cathodic materials because these are less expensive. Benaissa. In fact. Kim. use a solid reductant as the anode and a solid oxidant as the cathode such as LiS2. the new type of metal hydride particle is composed of a composite-like structure with two components (metal hydride + nickel). and AB5 type alloys are suitable materials for use as anodes in rechargeable NiMH batteries due to their high electrochemical capacity and excellent cycle life. et al. oxides allow the achievement of higher voltages than sulfides because higher cation valence states can be achieved in oxides (Wakihara and Yamamoto. there is much interests in using new oxides solely to lower the cost and reduce environmental concerns. which constitutes an assemblage of many individual nanofibers with diameters from 5 to 25 nm. A number of studies have shown that certain intermetallics such as the nanocrystalline AB. et al. et al. 1999) and carbon anodes. et al.. these ultrafine particle-size materials must still be agglomerated to become useful battery materials. et al. et al.. et al. Mechanical milling has been introduced by Jung (Jung. The present day lithium batteries. DeGuzman.. Due to the extremely low conductivity observed in manganese oxides. et al. however.. 1994.packing density than other conventional materials. the lithium metal anode was replaced by a second intercalation electrode. Easier hydrogenation behavior is believed to be a consequence of ball milling with pure nickel. 1994. 1999) and spinel Mn2O4 (Molenda.. however.2.. thus producing a composite-like structure (ZrCrNi + nickel) and nanocrystalline ZrCrNi. et al. 1992. 11. et al. Ohzuku.

1998) have resulted in the formation of nanocrystalline or amorphous oxides that were generally metastable.(M = V. petroleum coke. Recently. LiNO2 and LiMn2O4 (Nishizawa. and W) under aqueous conditions to obtain binary or ternary oxides MxOy and AxMyOz (A is Na or K). 1994) and LiMn2O4 nanotubes coated with PPy (Kuwabata.. It is common among many types of carbon electrodes used in batteries (Flandrois and Simon. Kuwabata. et al. 1995. This was shown by the increase in energy capacities of the electrode with decreasing oxide grain size. 1997. The carbon (graphite. 1998) can enhance performance. 1992) that the morphology of LiMn2O4 plays an important role in its electrode properties. et al. these represent examples of true organic/inorganic hybrids in "nano" scale as they basically comprise conductive organic polymer chains interleaved between the atomic sheet structure of a layered inorganic oxide or sulfide lattice... Mn. et al. 1996). the Li+-ion mobility and rate capability can be increased by keeping the particle sizes of the electrode materials small.. Alkali-metal borohydrides ABH4 were frequently engaged to reduce [MO4]n. Polypyrrole is an electronically conductive polymer and the support of PPy on high surface V2O5 aerogels (ARG) composites (Wong. a composite electrode such as graphite + acetylene black is used. and the prepared composites had enhanced specific capacities compared to the oxides mixed with carbon powder. it has been demonstrated by Tarascon and co-workers (Tarascon et al. the incorporation of transition metal oxide particles into conductive.. It must also be noted that the physical properties of these "nanocomposites" are very different from the "microcomposites" prepared by an alternative route. The nanocrystalline or amorphous nature of these materials is exceptionally attractive for achieving better lithium ion diffusion.. Examples of the resultant materials comprise of PPy/MnO2 composite films (Gemeay.. Kuwabata. Shokoohini.. The choice in the use of carbonaceous materials for anodes matches the current trend towards high performance cathodes such as LiCoO2. et al.. the electrode structure of the LiMn2O4/PPy composite can be made in nanoscopic scale. et al. In hard carbons.. 1999) that most of their structurelie in the nanoscopic scale. 1997) was carried out. To further improve on the charge/discharge performance. It was found that in comparison to the pristine V2O5 electrode material. Yoneyama. 1994.. Most importantly. Cathodes based on the creation of inorganic/organic hybrid structures that exhibit cooperative interaction among their constituents are hopeful candidates for use in Li-ion batteries. 1991. i. it is believed that lithium can be adsorbed onto the internal surfaces of nanopores. et al. et al. et al. Cr. The synthesis of transition metal oxides is usually done at ambient temperatures in solutions employing reducing agents. 1999).. in which the oxide gel is formed in the presence of preformed micrometer-sized polypyrrole particles.) electrode offers good cyclability owing to the formation of a e-/Li+ conducting passivation layer in organic electrolyte solutions. the underlying electrochemical response of these nanocomposites is synergistic in nature. 1991). Li-insertion studies have shown that these interesting composite materials act as conducting networks as well as active materials which ultimately enhance the electrochemical response. they show improved performance greater than the sum of the two components (inorganic and organic).e. Normally. et al. Mo. electrochemical insertion of Li into a series of "nanocomposites" composed of alternating V2O5 sheets and conductive polymer layers such as polypyrrole (PPy) and polyaniline (PAN1) (Leroux..Composites of manganese oxides particles and polypyrrole (PPy) have been attained by the addition of pyrrole into acidic aqueous suspension of the oxide (Gemeay. In fact. redox-active polymers has been proposed (Shouji. Such reduction methods (Tsang. which are formed by the layers of graphene sheets arranged like a "house of cards". In addition.. Since safety measurements have led to replacement of pure lithium by 60 . 1995. the incorporation of polymer enhanced the reversibility of Li insertion and thus increased the Li capacity in the nanocomposite. etc. et al. In. et al. et al. 1997).

Lastly. and also the Li2O plus other oxides playing the role of a "matrixglue" 61 .. Liu. et al.heavier carbonaceous materials with the general formula LixC6 as the anodes for lithium batteries. New forms of carbon can appear.. 1995b.. The discovery of carbon nanotubes (Iijima. 1996) is greatly reduced if the silicon host particles are nanometers in size. providing a large surface area for chemical reactions to occur (Megahed and Scrosati. 1998) for use as cathodes. and investigations showed that they could be promising battery materials for low drain devices. The concentration of lithium ions which can be inserted into the electrode would thus depend on the number of carbon nanobeads per unit area of the electrode.4 lithium atoms per silicon atom. like fullerenes and nanotubes (Flandrois and Simon.. Among these patent and literature reports. coals as starting materials have been proposed by Zheng et al. 1995c) than those currently employed as anodes in commercially available balleries. Strictly. Furthermore.. in an effort to make the carbon anode as inexpensive as possible. nanoscale. 1997b. (Zheng. 1991) led to their applications as support matrices for the preparation of one-dimensional. 1996). any loss in energy density due to this replacement has to be minimized (Peled. Sato. a high volumetric energy density is expected because silicon crystals can be intercalated to a maximum of 4. such repulsive forces among the ions would be avoided. The key reasons for the success are the finely dispersed tin regions. Sonobe. 1996). several tin-oxide-based compounds have been reported (Idota. Studies of disordered carbons containing nanodispersed silicon have also been presented by various groups (Wang. The requirement for a battery electrode is that it must intercalate a cation (Li+) with the release or uptake of an electron rapidly. the crumbling rate of alloying materials due to the large volume expansion during lithium insertion and brittleness of the intermetallic Zintl phase (Yang. Recently. Spherical spongy nanobeads as small as 250 nm have been prepared from camphor and the average surface area determined to be 16 m2/g. et al. depending on their helical structures and tube diameters. However. Graphite. et al. 1999). Carbon is a very versatile element.. 1997a. et al. Since the carbon nanotubes can provide pathways for Li diffusion into the crystal lattice of CuO copper oxide/carbon (CuO/C) composite nanotubes have been prepared (Wu. 1995a. Many groups have tried to search for materials with larger specific capacities (Yata. The extent to which lithium ions can be interled between two consecutive layers of graphite is limited by the repulsive forces created between the positively charged lithium ions. 1994. Idota et al. 1998. The large surface area of a mat of nanotubes is favorable to kinetics. et al. carbon nanobeads are becoming increasingly important as anodes and catalysts. et al. Zheng. the nature of chemical bonds between carbon atoms themselves or with other elements are varied. but the closed nature of the graphitic sheets may inhibit the process. a 1-D metal cannot exist since the Jahn-Teller (Peierls) distortion would give rise to a periodic change in bond length and a band gap. the passivation layer of the carbon decomposes leading to possible battery failure.. et al.. et al. 1998) showing that Si atoms or clusters of Si atoms can be embodied into these poorly stacked regions of the carbon structures for materials to reach working capacities near 500 mAh/g. 1995). at higher operating temperatures. et al. 1994. Brousse. et al. Besides. as a 2-D conductor. Nanotubes (Calvert. et al. if they can be inserted individually into nanosized hollow beads. however. However. is metallic. but the conductivity is poor compared with metals. It was suggested that this material could be very useful anodes for anodes in secondary lithium batteries.. 1997) has described how composite glasses based on tin-oxides can be used as high capacity anodes in Li-ion cells.. 1997) are expected to fall between the band gaps of 0 to 3 eV. 1994b. 1997. Courtney and Dahn. et al. et al. 1997. composite structures such as carbon nanotubes coated with nickel (Li. primarily responsible for the reversible reaction with Li. Alternative host materials such as nanocrystalline TiO2 (anatase) have also been proposed and studied by Huang (Huang. 1995).. 1997). 1994a.. 1998) to be good candidates for anodes in lithium-ion batteries instead of the carbonaceous electrodes. Among the various forms of carbon.

et al. 1993. so that the Li-Sn clusters and the composite glass matrix in which these reside are not broken up. 1981. To refine the morphological and electrochemical properties of polymer electrolytes. the Sn oxide-based anode has a large irreversible capacity resulting from the Li reacting with the oxygen bonded to Sn to form Li2O. et al.2 Electrolyte Today's Li-ion batteries use a polyethylene-polypropylene (PE-PP) film structure to separate the electrodes.. et al. future versions will focus on polymeric films which will display better stability at higher voltages or temperatures such as polyvinylidene fluoride (PVDF). loss of contact and poor capacity retention as a function of cycle number (Boukamp. structural changes such as fracture of the material. 1982) promoted by the network of the fillers into the polymer bulk and high ionic conductivity promoted by the large surface areas of the well-dispersed fillers make the composite electrolyte unique. 11. 1996) by employing mechanical alloying techniques (Cock. various highly conducting ceramic fillers. Excellent mechanical stability (Weston and Steele.. The addition of ceramics like alumina (Al2O3) (Croce. et al. Borghini. et al. 1995). 1996) when in contact with the lithium electrode. addition of ceramic fillers has been suggested. Capuano. 1999a. et al. then the bulk phases of Li-Sn alloys do not occur (Cock.. First. However. The Sn-Fe-C ternary alloy system has been recently investigated (Mao. polyacrylonitrile and polyethylene oxide (Mason. However.holding the particles together. Up to date. etc. the sizes of the Sn grains can be very small. 1999). The correct choice of a polymer matrix is very important in the cell's manufacturability and its longevity under strenuous operating conditions. et al.. 1993). Nanometer-sized grains of an alloy which would react with lithium (forming the "active" phase) are dispersed in an electrically conductive matrix of nanometer-sized grains of another phase which cannot react with lithium (the "inactive" phase).2. serve to act as a matrix to hold the active grains as they repeatedly alloy with lithium during operation. Wang. The inactive grains. In order to reduce the irreversible capacity. where elemental powders of Sn. Brandt. Whenever different bulk alloy phases coexist in the same grains. 1993) and the Li: Sn ratio in the cluster can vary continuously. 1993) as well as their interfacial behavior (Croce and Scrosati. Fe and. et al. zeolites. Claimed to possess both greater volumetric and gravimetric capacity over the graphite anode (Retoux.. 1986) are bound to occur.3. Nanometer-sized ceramic powders can act as plasticizers for PEO and kinetically inhibit crystallization upon annealing from the amorphous state.. 1995. Further reaction then occurs between the newly created metallic Sn with Li and leads to the formation of Li-Sn alloys. the Sn oxide in the composite reacts with Li to form amorphous Li2O and metallic Sn. The electrochemical reaction occurring in these compounds is not the intercalation of lithium into the host structure.. but follows a two-step reaction process of Li with the tin oxide-based composite glass. the crystal structures of bulk Li-Sn alloy phases have different lattice constants and different volumes per tin atom.. 1994). 1998) facilitates an improvement in conductivity of poly (ethylene) oxide (PEO)-based electrolytes (Lightfoot. et al. oxygen bonded to tin should be avoided in the material. particle size and content of ceramic appear as critical factors.. ionites. these tin oxides are also stable in air and standard electrolytes. C are mixed mechanically in high-impact ball mills to give mixtures of coexisting intermetallic phases with very small grain sizes. In all cases. Unfortunately. It is also clear that the mechanical and electrochemical properties of electrolytes will improve as the grain size of ceramic particles used is descreased. which is structurally benign (Nagaura and Tozawa. if very small grains of tin (in nanometer sizes) are formed. Depending on the composition of the tin oxide-based composite. with the 62 . Good capacity retention during the charge-discharge cycles can then result. have been investigated (Nazar. 1990. Unlike intercalation. 1999). hence.. Thus the reversible reaction in the anode is essentially the alloying and dealloying of Li with the very small grains of tin.

or insertion of Lithium into carbon host lattices avoids the problem of lithium dendrite formation. This has led to many prototypes of carbon-based lithium ion batteries developed since 1990 (specific energy densities as high as 340 Wh/L) Since reversible intercalation. et al. Instability of these electrolytes caused mainly by high temperature or voltage may be detrimental to the operation of the battery. It is well known that undoped BPO4 has been determined as the high-cristoballite structure (Schulze. Long. Solid-state materials in the form of pastes are applied to the polymer film and the electrolyte made thin enough to compensate for the reduced ionic conductivity of polymer compared to the liquid electrolytes. et al.. 1934. 1992. all the B and P ions are tetrahedrally coordinated by O ions and each O ion is shared by two tetrahedra. 1998.2. The challenging concept in secondary lithium batteries lies in the removal of the dendrite regrowth problem. Vaia. the particles added are so fine that a large volume of the solid mixture consists of grain boundaries. Giannelis and co-workers (Giannelis. Furthermore. 1996) demonstrated the use of Li-doped BPO4 as a Li-ion conducting electrolyte for Li batteries. 1975) since the late 1930s. The majority of the publications on solid-state battery electrolytes are based on the polymeric electrolytes used.main contributing factor being that the conductivity is closely linked with the processes occurring at the grain boundaries. a reduction of the ceramic powder particle size from microns to nanometers should lead to further increase in the conductivity as well as reduced weight. In their work based on mica-type ceramics. Subsequent investigations made by Jak and Kelder (Jak. a copolymer gel electrolyte based on polyacrylonitrile (PAN) for the development of the Li-ion-P battery is being studied by Sony Corp. et al. 1993) created a new type of layered nanocomposite polymer electrolytes of single conductivity.4 Most Recent Developments A prototype Li-ion polymer cell based on a solid-state conductor where electrodes and the electrolyte were embedded in a flexible plastic matrix has been developed by Institute for Silicon Technology(ISIT) (in collaboration with the Christian Albrechts University.. 1999) reveal that the total ionic conductivity increased with decreasing grain size.3 Fuel Cells and Nanomaterials 63 .. in which its conductivity is comparable to the state-of-art polymer-based electrolytes. Currently. 1980. the isomorphous substitution of silicon by aluminium led to immobilized and highly delocalized charge balanced by lithium ions present in the nanosized galleries infused with PEO polymer chains. and a maximum in total ionic conductivity was shown at doping levels of 7 mol% lithium. In. 11. 1996. This indicates that the nanostructure of the ceramic electrolyte is vital for use in all-solid-state Li-ion batteries. In these polymeric nanomaterials. Since polymer nanocomposites that consist of just a few percent of ceramic particles can behave like other conventional microcomposites that have 60%—70% ceramics in them. According to this structure. ceramic electrolytes have also been identified. Kosten and Arnold. Thus. such as Li-doped BPO4. Germany). The ionic conductivity mechanisms were proposed to take place via the interstitial Li ions as the defect chemistry of the BPO4-xLi2O structure was studied. Kelder and co-workers (Kelder. 11.

Solid polymer electrolyte (SPE) Aqueous alkaline Molten carbonate Solid cxide 11. Phosphoric 2. The solid polymer electrolyte (SPE) cell uses an ion exchange membrane as the electrolyte and is thus called a proton exchange membrane fuel cell (PEM-FC). There are essentially two types of acid fuel cells. usually determined by the various combinations of the type of fuel and oxidant. Platinum or platinum alloys (in very small quantity) as the active electrocatalysts.1 Acid and Proton Exchange Membrane Fuel Cell (PEM-FC) The acid fuel cell can be characterized by: 1. thus eliminating the need for a separate fuel processor with its ancilliary equipment.1 Classifications of Fuel Cell Systems Fuel cells can take on several different configurations. In general. etc.3 Classification of fuel cells Fuel Direct Hydrogen Hydrazine Ammonia Hydrocarbon Methanol Natural Gas Coal Oxidant Indirect Hydride Ethanol Ammonia Hydrocarbon Methanol Coal Oxygen Oxygen(air) Hydrogen Peroxide Temperature Electrolyte Low (120°C) Intermediate (120–160°C) High (260–750°C) Very high (≥750°C) Aqueous acid 1. new approaches are being evaluated that would allow future PEM fuel cells to operate with fuel gases containing CO. Table 11. we have the following classification shown in Table 11. the type of electrolyte used.3.11. This also gives rise to the direct methanol 64 . Hydrogen ions [or by hydronium ions (H3O+)] providing the passage of ionic conduction. Reformation of natural gas or other fuels containing hydrocarbons can also be accomplished within the generator.1.3. 3. These are suited for low-temperature use. the way fuel is fed to the system (direct or indirect). Current collectors and gas separators are made of carbon (graphite). 1988) which will inhibit the fuel cell anode reaction. 2. These techniques involve the construction of new anode electrocatalysts and the control of external prehumidifying of air. Sulphuric 3. namely the solid polymer electrolyte system and the phosphoric acid cell. but are prone to poisoning by carbon monoxide (Parsons and VanderNoot.3. thus permitting the working temperature to be raised. Through the use of different materials. the operating temperature.

the other being the ability to work together with steam turbine generators. Methanol is easily transported and converted to energy from the liquid state. which comprises part of the fuel cell stack. The phosphoric acid electrolyte system is the most mature fuel cell technology and is commercially available now. 11. Several features of SOFC technology make it very attractive for industrial and utility applications. solid oxide electrolyte fuel cells utilize a nonporous solid oxide. This type of fuel cell uses liquid phosphoric acid as the electrolyte with hydrogen gas ionized at the anode to form hydrogen ions and electrons. At the anode. Successfully operating in Japan for a number of years. The fuel cell stack is made up of two porous electrodes in contact with a molten salt of lithium-potassium carbonate (LiKCO3). Steam and methane (the main ingredient of natural gas) are converted into a hydrogen-rich gas in the reforming anode or in a reforming chamber. while at too high temperature material stability of carbon and platinum becomes limiting. releasing two electrons.4 Alkaline Fuel Cells (AFC) 65 . as the electrolyte. Without the presence of liquid phases in the electrolyte. Oxygen ions from an air electrode (cathode) migrate through the solid electrolyte to a fuel electrode (anode). oxygen (O2) and carbon dioxide (CO2) are converted into carbonate ions. 11. operating at approximately 650°C. one being high tolerance to fuel contaminants. At the cathode. There. The electrons travel to the cathode via an external circuit while the hydrogen ions travel to the cathode through the electrolyte. hydrogen will react with carbonate ions to form water and CO2.1. they react with carbon monoxide (CO) and hydrogen (H2) contained in the fuel gas to deliver electrons and hence generate electricity. 11. the system does not need costly catalysts and allows direct processing in the fuel cells. usually doped with zirconia. It has a very high operating temperature (1000°C) at which the lattice structure of the electrolyte material becomes sufficiently conductive to oxide ions. Molten carbonate fuel cell plants can achieve an electric efficiency of 50%. thus pushing major technology in this area towards the improvement of cathode materials.2 Solid Oxide Fuel Cells (SOFC) As the name implies. The phosphoric acid electrolyte system operates at 150°C to 220°C since at lower temperatures phosphoric acid is a poor ionic conductor. many of the problems associated with electrode flooding. the current design possesses an electrical conversion efficiency of 41%. electrolyte migration and catalyst wetting are avoided. Because of the high operational temperature.3.3 Molten Carbonate Fuel Cells (MCFC) Molten carbonate fuel cells are a type of direct fuel cell that eliminates external fuel processors. The solid oxide electrolyte is very stable.fuel cell (DMFC) in which methanol is reformed to produce H2 and CO2.1.3.3. By completing the flow of electrons through an external circuit DC electricity is generated. The electrolyte allows carbonate ions to migrate to the anode.1. The cathode performance is usually sluggish.

The early alkaline fuel cells operated at relatively high temperature (≈250°C) with concentrated (85 wt%) potassium hydroxide. However. electrolytes. can be a winning choice of alternative next to batteries for long-term usage. directs the electrons to the external circuit)..g. The material compatibility imposes a primary constraint (Jensen. the alkaline systems usually feed on highly purified hydrogen gas from electrolysis or ammonia plants. ammonia. which can only be achieved by Pt metal clusters in the nanometers range. must provide the common interfaces for the electrolyte with the fuel and oxidant respectively. but the use of less concentrated (35 to 50 wt%) potassium hydroxide in recent alkaline fuel cells leads to a much lower operating temperature (<120°C). an important aspect in fuel cells. etc. The application of nanosized materials is. the oxidant-electrolyte interface must catalyze the oxidant reduction. the state-of-art technology of fuel cells in electric vehicles (EV) involves the incorporation of platinum loadings of no more than 3 µg/cm2. nanosized platinum particulates have been shown to offer substantial advantages concerning activity and lifetime in electrocatalysis. hydrazine. Metal hydrides are popular since they are able to store large amounts of hydrogen in a higher energy density (total equivalents of hydrogen per total mass of 66 . The O2 reduction process in alkaline electrolytes is more favourable than in acid electrolytes. therefore. gas separation is also provided by the electrolyte system. In the alkaline medium. At the anode.. The matrix may then act to separate the gases through the presence of capillary forces of the electrolyte within the pores. in which fuel can be introduced without the conversion to hydrogen. It is clear that the use of ultrafine catalytically active material dispersed in an appropriate electrode matrix is required to achieve the maximum current density per unit of projected electrode surface area. and conduct electrons from the external circuit to the oxygen electrode reaction site. the choice of catalysts used in alkaline systems is not solely limited to the platinum and tungsten carbides group. The electrodes. The electrolyte must act as a medium of transport for the ionic species involved in the fuel and oxidant electrode reactions while restricting the flow of electrons (conduction of electrons in the electrolyte causes a short circuit). carbon dioxide. Unlike acidic cells. In practical cells. Easily handled and readily oxidized fuels such as methanol. no acidic impurities. in turn. have been used in most fuel cells. The direct-type fuel cells. This is very detrimental to the stability of the alkaline fuel cells. This is accomplished by retaining the electrolyte in the pores of a matrix. 1982) on the construction of fuel cells. the fuel-electrolyte interface must provide good catalysis of the fuel oxidation reaction and conduct electrons from the reaction site to the external circuit (or to a current collector that. comprising both the anode (fuel electrode) and the cathode (oxygen electrode). and fuel supply/storage systems. Fuel cells. are presently attractive options for small fuel-cell systems. the presence of carbon dioxide results in the formation of carbonates which would block electrolyte pathways and electrode pores.2 Major Components and Nanomaterials in Fuel Cells Three important components of fuel cells are the electrodes. Today. e. in the power range of up to 200 W. Ammonia may also be used in direct fuel cells because the oxidation of ammonia to nitrogen and water occurs readily on noble-metal catalysts.3. are tolerated in either of the reactants. Being a necessity in the working of an automotive vehicle. In practice. Due its alkaline nature. Methanol and hydrazine are the main liquid fuels used. At the cathode. especially with potential reduction in the mass and cost. the majority of current portable fuel cell developments use a metal hydride as the source of hydrogen fuel. 11.

1989. Gottesfeld and Wilson. et al. Raney silver for oxygen cathodes in alkaline cells) were employed. proposed the use of conducting polymer/proton exchange polymer composites (Qi.3. usually achieved by covering the surface with a solution of solubilized membrane material such as Nafion (Yeo. 1992.. 1989. By the use of nanosized platinum metal clusters. 1994). Tarasevich and Radyushkina.g. Raney nickel for hydrogen anodes. highly porous metals (e. The carbon electrodes consist of soot agglomerates 100 to 500 nm in diameter while Pt or Pt alloys are uniformly dispersed on the internal surfaces of these soot particles (Faubert.. van Veen. Previously.. In the polymer electrolyte fuel cell. et al. A certain procedure of creating effective contact with the protonic conductor is by impregnating the supported-catalyst electrode with the protonic conducting materials. the effective surface area will be greatly increased. Wiesener. In the following... since it does not conduct protons and is impermeable to gases. However. solid membrane and phosphoric acid type are composed of the granular.. In this area of research. et al.. the trend is certainly to use the platinized carbon exclusively as cathodic and anodic catalyst for any type of low-temperature cells. the incorporation of carbon into the catalyst layer restricts the flow of oxygen. et al. Hence. et al. subsequent technical improvement of fuel cell electrodes was only possible because gas diffusion electrodes were developed with dedicated electrocatalysts having an efficiency of about 60% as compared with the theoretical efficiency of 80% (Wendt.. Initially.. Qi et al. the status of fuel cell technology with reference to nanomaterials is listed. 1990. et al. 1996) and achieve enhanced performance and weight advantage.1 Electrodes From the space fuel cell by United Technologies Inc. 1991. 1992a. The ideal catalyst support should be permeable to gas and water as well as capable of conducting protons and electrons. which have been shown to exhibit high electron and proton conductivities. 1992) based on organometallic 67 . the catalyst at the electrodes must have access to the gas and be in contact with both the electrical and protonic conductors simultaneously. Savy. Franke. 1998). et al. but recently. Widelöv and Larsson. such a material is liable to fully replace the carbon support and Nafion in the catalyst layer (Appleby.. nanosized electrocatalysts. 1986. Taylor. 11. In their work. et al.3 Applications of Nanomaterials in Fuel Cells 11. 1986. The primary role of the carbon support is to provide electrical connection between the widely dispersed Pt catalyst particles and the porous current collector (carbon paper or cloth)... 1998) dispersed on the surface of fine carbon electrodes).hydrogen source and container) than hydrogen stored in pressurized or liquefied form. they also produced large quantities of catalyzed polymer particles which could be incorporated into standard PEM fuel cell electrodes.3. but this problem was solved by the use of supported platinum catalysts similar to those in liquid-electrolyte fuel cells (2–3 nm diameter Pt particles (Dalmia. et al. high platinum loadings (typically 4 mg/cm2 of platinum) were needed for useful rates of hydrogen oxidation and oxygen-reduction reactions. 1998). 1983). such as polypyrrole/polystyrene sulphonate (PPy/PSS). 1992). focus is essentially on either reducing the Pt loading or replacing it completely by the use of non-noble metals (Scherson. 1992b. et al. 1988. and polytetrafluoroethylene (PTFE) as a hydrophobic binder. water and proton transport and limits the overall performance of the fuel cell. Biloul. These low-temperature fuel cell electrodes of the alkaline.3. experiments were carried out to replace Pt at the cathode by nanoparticle catalysts (Srinivasan. 1983. In the early 1990s.

However. et al. This was accomplished through the addition of zirconia corresponding to the formation of Fe0. 1994) as a gas requires large volumes of space and even under compression. 1978) hydrides. 1998a). et al. enabling the activation temperature to be reduced considerably (Singh. Moreover. Coupled with the extra mass from the storage cylinder. 1996). et al. any leakage of hydrogen will be suppressed through self-cooling. The volume efficiency can be improved by liquefied hydrogen. 1995. FeTi is an intermetallic Lave phase material. it was reported that catalytic decomposition of hydrogen in FeTi was possible. the challenge is to select the most appropriate metal hydride or some other material and to design the best storage vessel for a specific application. yet the energy required for liquefaction and the need for excellent insulation of the hydrogen containers to prevent loss of H2 over time become great disadvantages. An ideal solid for hydrogen storage would be a structure consisting of slit-shaped nanopores that have a width slightly higher than the kinetic 68 . The nanocrystalline structure is the key factor for achieving such a remarkable improvement in the hydriding of Mg2 Ni.. due to the large number of available materials and the different requirements for a wide variety of applications in fuel cells. At this end. 1997) produced by the carbon arc method as the catalysts for electroreduction of oxygen in PEM-FC and activated this material containing 17. In 1997. New hydrogen storage materials for improved hydrogenation characteristics. The resultant nanoparticles yielded a higher hydrogen storage capacity due to the increased surface area corresponding to smaller particle sizes. Recently.. Therefore. reaction..3. such as the synthesis of Mg2 Ni (Zaluski. The formation of the hydride is an exothermic.2 Ti1. scientific problems involving its storage must be addressed. Today. liquid or in easily dissociated compounds such as metal hydrides.compounds absorbed on carbon black (Dodelet. 1994) and pyrolyzed at various temperatures. since hydrogen recovery is endothermic. et al. Keskinen and Ruuskanen. The amount of hydrogen that can be stored with respect to volume is much more efficient than liquid and gas. its activation is rather difficult and research work is required to make the activation process amenable.8 Zr0.2 Hydrogen Storage In order to evaluate the possibilities of achieving hydrogen utilization in a fuel cell (Appleby and Foulkes..3. used carbon-coated fcc cobalt nanocrystallites (Dodelet. gaseous storage becomes a major disadvantage.0 wt% Co by a pyrolysis step at 1000°C. Still one of the well-known hydrogen storage materials currently. the metal hydrides that received the most attention and showed the highest potential applications were FeTi and LaNi5 (Busch. The storage hydrides are customarily safe and stable when under their dissociation temperatures. Hydrogen may be stored as a gas. the storage of hydrogen as metal hydrides becomes one of the most promising alternatives because of its unique feature. Dodelet et al. The storage of hydrogen (Riley. 1989). 11. In the early years.. usually spontaneous. was accomplished by ball-milling of a correct stoichiometric mixture of magnesium and nickel. while the reverse hydrogen recovery can also be easily achieved by heating the hydride. the volume efficiencies cannot match those of liquid hydrogen.3. They found that catalysts obtained by the pyrolysis of the organometallic precursors at high temperatures (≥800°C) were very efficient and stable at the same time. metal hydrides have a better reversibility of the formation reaction compared to water (which forms H2 and O2 by electrolysis). et al.

1998) uses methanol as fuel and is mainly based on a solid polymer electrolyte.3. 1998).. Therefore. Che. 1998. e.. Figure 11. The direct methanol fuel cell (DMFC) (Scott. metal-intercalated graphite has been considered as a possible candidate for hydrogen storage. This unique conformation bestows upon this material the excellent qualities which are very much desired for gas sorption applications.7. where platelets generate a system comprised of entirely slit-shaped nanopores and the short diffusion path..337 nm is facile. et al.3 Reforming In addition to the practice of fuel cells feeding on pure hydrogen. et al. 11.3 to 50 nm in width and are stacked in a perfectly arranged conformation as shown in Fig. have been intensely studied for hydrogen storage purposes (Rodriguez. it is necessary to develop a simple system which can removed CO to less than 100 ppm (Gottesfeld and Pafford.diameter of hydrogen. any other carbon-containing fuel creates the possibility of separating carbon dioxide and either reusing or disposing of it. The anode catalyst is very susceptible to poisoning by the carbon monoxide (CO).3. which may remain in the reformed gases up to 100 parts per million (ppm). a novel type of carbon material. Chambers. the sorption of molecular hydrogen in the interplanar distance of 0.g.7 (a) Schematic representation of the arrangement of platelets in catalytically grown graphite nanofibers. 11. Due to the unique crystalline arrangement existing within the graphite nanofiber structure.. 1997. Research has indicated that this material is capable of sorbing and retaining in excess of 20 L of hydrogen per gram of carbon when the nanofibers are exposed to the gas at pressures of 120 atm (1 atm=1. In addition. As such.. 1988. being 0. This storage volume is of a magnitude higher than that with the conventional hydrogen storage systems. 69 .3 nm. Dillon. GNF are produced from the dissociation of carbon-containing gases over selected metal surfaces. (b) An enlarged section showing the details of area marked in (a). or in fact.01 × 105 Pa) at 25°C. 60–80°C. 1990) in large excess of H2. 1995. reformed gases from methanol or natural gas may also be used. The nanofibers consist of very small graphite platelets. the weak van der Waals bondings of the platelets allow the nonrigid wall nanopores to expand to accommodate molecular hydrogen in a multilayered configuration. Reforming to produce hydrogen gas from natural gas. The PEMFC functions at relatively low temperature. graphite nanofibers (GNF). et al. 0. et al. et al. Gottesfeld.. In recent years.

e. 1995). Dupont de Nemours. et al. however. Ross. 10 times larger than the selectivity of the conventional Pt/Al2O3 reported. et al. 1992.. i. et al. 1999) recently suggest that these are primarily a mix of Pt metal and the oxides of Ru. Therefore. especially at the reactive α-H sites where the functional groups are attached.. bulk and surface analyses (Rolison. Vanderborgh. RuO2 · xH2 O or RuOx Hy have been detected in the lilevature. The presence of the hydrous oxide with RuOx Hy rather than Ru metal or anhydrous RuO2 proves to be an efficient catalyst for oxidation of alcohols and more chemically durable under corrosive conditions. Yeo and Eisenberg. the polystyrene-based sulphonic acids are replaced with fluorine substituted polystyrenes (e. Other research groups have suggested that alloys of Pt with more oxophilic elements (Koch. the world's leading perfluorosulphonic polymer electrolyte is Nafion produced in 1962 by E. they cannot be discerned by X-ray differaction. et al.3. 1980. polytrifluorostyrene sulphonic acid).4 Proton Exchange Membranes The proton exchange membrane fuel cell utilizes an ion exchange electrolyte which is an excellent conductor of protons. this material consists of a fluorocarbon polymer backbone. the hazard of accidental explosion cannot be ignored.Oxidative elimination of CO was proposed using Pt catalyst supported on alumina (Pt/Al2O2-3) in the presence of 2% oxygen or air (Cohn. tubes and solutions. nanocrystalline composite oxide SrRuO3 (with a perovskite structure) can partially substitute platinum as a catalyst in methanol oxidation with improved features such as better performance and lower cost. Bonacci. However. 11. showing high conductivity (see Figs. Thus. Since the problem lies in the poisoning of the catalyst surface by carbon monoxide. Hence... 70 .. It was found that composite oxides with the perovskite structure are good catalysts for complete oxidation of methanol because electrons on the d-orbitals are always available for transit and are in the high-spin state. catalysts comprised of highly dispersed metals such as platinum in A-zeolite were reported by Watanabe and coworkers (Watanabe. plus some Pt oxides with little Ru metal. powders. The synthesized catalyst consisted of Pt nanocrystallites dispersed on A-zeolites and showed exceptionally high selectively for the oxidative elimination of CO present in the 1% mixed gases with an excess of H2.. 1965. X-ray photoelectron spectroscopy (XPS) and Mössbauer studies have been conducted and the substantial amounts of hydrous ruthenium oxide. To say the least. The acid molecules are anchored to the polymer and cannot be leached out.g.. 1995) can be active for direct methanol oxidation. in order to avoid this. 1999). 1988). 1982. Today. similar to Teflon PTFE (polytetrafluoroethylene) to which the sulphonic acid groups have been chemically bonded. yet is an electronic insulator.3.. Several studies on the structure and properties of Nafion have been reported in the past two decades (Pineri. 1994. composite oxides as catalysts have been reported (Zhao. the hydrocarbon-type polymers are easily subjected to oxidation due to the C-H bond cleavage. but the protons on these acid groups are free to migrate through the electrolyte. Such a catalyst was able to oxidize CO selectively in reformed gases. I. since the O2 content present is close to the lower limit for explosion of mixed gases. 1964) such as Pt-Ru oxide blacks (Gurau. of key importance to the mechanism of methanol oxidation is that hydrous ruthenium oxide is a mixed proton-electron conductor. Examples of the early membranes tested include the hydrocarbon-type polymers such as crosslinked polystyrene-divinylbenzene sulphonic acids and sulphonated phenolformaldehyde. the configuration and geometry of the nanosized ion aggregates within the conducting matrix are still being debated. 1987. 1977). However. 1998. It is commercially available in various forms: homogeneous or reinforced membranes. However. et al. However. Freelink. These nanoscale Pt-Ru blacks are widely accepted to be bimetallic alloys based on their X-ray diffraction patterns. Due to their amorphous structure. et al.

11.8 and 11.9). The Nafion membrane is very stable and strong, has an equivalent weight of 1100 and when saturated contains 25 molecules of water per SO2-3. At least four grades of Nafion are currently available: 117, 115, 112 and 105 (Kordesch and Simader, 1996). The initial two digits indicate equivalent mass, e.g., 1100. The last digit represents the dry thickness in mils (e.g., 7 mils or 175–180 µm). Similar ion conducting membranes are available from Dow Chemical Company (m = 0, n = 2, equivalent mass 800, normally 125 µm thick) with m and n as denoted in Fig. 11.8. Another homologous series, Aciplex-S from Asahi Chemical Industry Company, in which m is 0–2 and n is 2–5, is also known. These materials are synthesized through slightly different chemistry and possess slightly different properties having equivalent mass of 1100, 800 and 1000.
Figure 11.8 Structure of perfluorocarbon ion exchange polymers.

Figure 11.9 Schematic representation of ion clustering in Nafion

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One key technological problem in PEM-FC is the water content management and reactant crossover problem (Verbrugge and Hill, 1990; Zawodzinski, et al., 1993; Fuller and Newman, 1992). During operation, polymer electrolyte membranes such as Nafion require water to maintain their protonic conductivities. However, the water content is changed in an extremely complicated manner with the operating conditions and further discussion is beyond the scope of this chapter. In practical use, the water content in PEMs can be indirectly controlled by humidifying either the fuel gas or the fuel and oxygen. By reducing the polymer electrolyte thickness, water management problems due to the water back-diffusion from the cathode (Springer, et al., 1991) are distinctively reduced, due to a decrease ohmic potential drop in the cell while improving cathode performance (Watanabe, et al., 1994a). However, this usually accelerates the crossover of H2 and O2 through the thin electrolyte membrane and leads to lower cell performance and fuel utilization. Attempting to address this problem, new polymer electrolyte membranes with highly dispersed nanometer-size Pt and/or metal oxides such as titanium dioxide powders (Watanabe, et al., 1994b, 1995a) have been proposed. In 1998, a design concept for the Pt and metal oxides dispersed PEM (Watanabe, et al., 1998) shown in Fig. 11.10 was proposed. Platinum nanocrystals (d is 1–2 nm) were highly dispersed in a Nafion 112 film (Pt-PEM, thickness 50 µm) to catalyze the recombination of the crossover H2 with O2, and the water generated was found to humidify the Pt-PEM direct fuel cell. The Pt particles were expected to inhibit the crossover of the gases by the catalytic recombination of O2 and H2, while the oxide particles (with hygroscopic property) were expected to adsorb the water produced at the cathode reaction, releasing it only when required. In this work, the self-humidification behaviour of Pt-PEM, TiO2-PEM, and Pt-TiO2-PEM prepared by the dispersion of small quantities of Pt particulates (1–2 nm dia.) and/or TiO2 particles (5 nm dia.) in Nafion 112 recasted film (50 µm thick) was investigated. In particular, the Pt-TiO2-PEMs show that the crossover H2 and O2 was able to recombine on Pt particles and all the moisture generated inside the PEMs was exhausted from the anode. Being hygroscopic in nature, the TiO2 particles enhanced the back-diffusion of water produced by faradaic reaction at the cathode and resulted in very efficient
72

humidification of the PEM of the anode side dried by the electro-osmotic drag. Overall, the novel PEMs were found to improve the cathodic potential and demonstrated superior performance in which the suppression of the crossover of gases under the unhumidified environment was comparable to that of the conventional (humidified) case. This also suggested the elimination of any short-circuit reaction of the crossover gases in the cathode catalyst layer and thus the non-faradaic consumption of H2 was reduced without any disturbance of O2 diffusion by the produced water vapor.
Figure 11.10 Schematic operation concept of the PEM-FC using self-humidifying Pt-oxide-PEM.

In recent times, as an alternative to ionic conducting polymeric electrolytes, a bicontinuous structure made by the microemulsion technique has been proposed (Chow, et al., 1999). Microemulsion systems are thermodynamically stable, isotropic assemblies of oil and water, separated by an interfacial film of surfactant molecules (Friberg, 1983; Langevin, 1988; Paul, et al., 1997). Depending on the composition of oil, water and surfactant, the formation of microemulsions can be in the form of water-in-oil droplets or oil-in-water droplets. In addition, there may exist bicontinuous microemulsions in which the oil and aqueous conduits (channels) are randomly interconnected forming sponge-like structures. The oil phase can then be polymerized together with the polymerizable surfactant (Gan, et al., 1995), and the water phase be treated to host ionic species. With the copolymerization of ionic monomers, such as 4-vinylbenzene sulfonate (SVBS), in the polymerizable microemulsions, ionic conducting membranes can be produced. The resulting material provides great potential for use in ion exchange polymers as the bicontinuous structures prepared from the microemulsion techniques contain mobile cations which are counterbalanced by the sulfonic groups anchored to the PEO backbone of the polymer. The most probable pore sizes (in diameter) were found to be less than 8 nm. The pore volume distributions also become narrower with increasing ionic content in the microemulsion system. Similar to Nafion, these nanosized aqueous pores found in the styrene-sulfonate microemulsion membranes are crucial to the ionic transport. The conductivities reached 10-3 S/cm which are much better than conventional PEO (doped with salt) type polymer electrolytes. Due to the nature of the microemulsion technique, many parameters can be fine-tuned in the future improvement of the membrane.
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For example, the oil phase may be modified to increase the thermal, mechanical and chemical stabilities, whereas the aqueous phase can be modified to host various ions and to remove the frozen state. New technological applications in electrochemical devices, including electrochromic displays, chemical sensors and fuel cells, suggest demand for high temperature protonic conducting membranes. Organic/inorganic nanocomposite materials which show high ionic conductivities at temperatures in excess of 100°C, are good candicates for high temperature membranes. These solid nanocomposite membranes belong to a remarkable family of isotropic, amorphous materials with excellent thermal properties, electrical conductivities, flexibility and mechanical strength. Synthesized by sol-gel processes, these properties including optical density can be carefully controlled through the adjustment of the compositions, nanophase size and chemical bonding between the organic/inorganic composite membranes. A specific example is the organic/inorganic nanocomposite membrane consisting of SiO2/PEO which showed good protonic conductivities and thermal stabilities up to 160°C. It was synthesized via a sol-gel method (Honma, et al., 1999). The composite membrane was obtained by hydrolysis and a condensation reaction of polymer precursors consisting of polyethylene oxides endcapped with trioxysilane and further subjected to doping by acidic surfactant molecules MDP. The hybrid membrane had a structure of an interpenetrated network composed of a nanosized mixture of silica (silsesquioxane, Si2O3) and PEO, with each silica domain restricted to a distance of approximately 3 nm by the chemically bound PEO chain. Because of the presence of inorganic silica as part of the structural elements, the composite membrane showed high temperature tolerance. Thus, the properties of such hybrid membranes can be designed through delicate manipulation of the compositions of the components containing nanosized composite structures among the organic PEO, inorganic silica and functionally doped MDP.

11.3.3.5 Solid Oxide FC Membranes
The task of developing electrolyte membrane for the solid oxide fuel cell (SOFC) (Watanabe, et al., 1997), expected for future electricity generation, will be a demanding one due to the need to simultaneously satisfy electrical, chemical and thermomechanical requirements. Usually, the electrolyte is zirconia (ZrO2) doped with 8 mol%-10 mol% yttria (Y2O3). Pure zirconia is an insulator. However, when doped with yttria, some Y3+ replaces Zr4+ in the fluorite-type crystal structure and results in a number of vacant oxide-ion sites. These sites become available since three O2- replace four O2- when two Zr4+ are replaced by two Y3+ in the lattice structure. As such, the mobile ionic species O2- can move across the electrolyte via the vacant lattice sites at high temperatures and conduct charges. The current carrying O2- species arrive at the electrolyte-electrode interface and react with the gas phase within the porous electrode to generate electricity. A representative electrolyte material such as 8 mol% Y2O3 stabilized ZrO2 (8YSZ) possesses low electronic and high oxygen ionic conductivity. Although the traditional thin-layer 8YSZ can show excellent electrical properties at 1000°C, this oxide-ion-conducting electrolyte possesses poor mechanical properties, such as low strength, toughness, Young's modulus and thermal conductivity (Minh, 1993; Isaacs, 1981). Hence, to broaden its use at high temperatures, some improvements must be made to 8YSZ. Current studies to improve the mechanical properties of zirconia and other ceramics are directed at using phase transformation as well as composite techniques. The phase transformation of zirconia from tetragonal to monoclinic (Claussen, 1984; Masaki, 1986; Tsukuma, et al., 1988), however, may not be as effective on strengthening
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and toughening of the material at elevated temperatures (Masaki, et al., 1986). The latter method of strengthening by dispersing particles, whiskers, platelets or fibers into the electrolyte is undoubtedly more effective. In particular, ceramic-based nanocomposites such as the ceramic/ceramic and ceramic/metal composite systems have attracted enormous attention as particle-reinforced composites, in which nanosized second phases are dispersed within the matrix. The random dispersion of the second phase nanosized particulates improves not only the mechanical properties but also functional properties. In fact, attempts have been made to fabricate 8YSZ/silicon carbide (SiC) nanocomposites by a hot-pressing technique (Bamba, et al., 1998). The effects of dispersed nanoparticles of SiC on the microstructures of the material and the resulting ionic conductivities have been investigated. It was found that ultrafine SiC particulates inhibit the densification process and normal/abnormal grain growth of the 8YSZ matrix grains occurred with decreases in grain boundary diffusivity and mobility. As the SiC content was increased, the inhibition phenomenon became more obvious although the nanocomposites still retain a fine and homogeneous microstructure. The total conductivity, however, decreased with increasing SiC content due to the decrease in grain boundary conductivity, which must be related to the increase in grain boundary length and the decrease of effective volume of ionic conductor by SiC particles at the grain boundaries. Apart from the Y2O3 stabilized ZrO2/SiC nanocompsites, other rare-earth and calcium doped zirconates are also materials of choice for electrolytes used in intermediate temperature solid oxide fuel cells. The dopant, in each case, serves not only to stabilize the cubic structure of zirconia but also to introduce and create anion defects which presumably increase the ionic conductivity. Efforts to develop new oxygen ion conductors with enhanced properties have spurred the development of many potential electrolyte materials for use in solid oxide fuel cells. Alternatives to zirconia, e.g., Bi2O3-and CeO2-based materialss were proposed. In the past, ceria-based (CeO2-x) materials were extensively investigated as catalysts, structural and electronic promoters of heterogeneous catalytic reactions and oxide ion conducting solid-state electrochemical cells. To date, research on ceria solid electrolytes doped with small amounts of Pr or Tb as electron traps to extend the oxygen partial pressure has been carried out (Greenblatt, et al., 1998). Beside, other rare-earth elements such as samarium have also been investigated extensively (Watanabe et al., 1997). Prepared hydrothermally, the average crystallite size of samarium-doped ceria powders (7–68 nm) enables sintering into dense ceramic pellets at 1400°C. Compared with zirconia, the ionic conductivity was high (→ 10-2 S/cm) even at an operational temperature of only 600°C.

11.3.4 Summary
Fuel cells will play a key role in the future world energy scenario. Their most important characteristics, namely high efficiency and extremely low emission and noise levels, will be mandatory in the next generation of power plants. Should hydrogen be the main energy carrier of the 21st century, as many technical studies point out, then fuel cells will have many undisputed advantages over all other energy conversion devices.

11.4 Conclusions
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The most pressing need for research in energy conversion for the next century will be to meet the different challenges in the ways of generating or storing electric power in a more efficient as well as environmentally benign way (Kartha and Grimes, 1994). Today, new possibilities and opportunities have opened up by timely nanotechnology in the synthesis of materials that can be engineered for the efficient functioning of batteries and fuel cells. Clearly, the ongoing research projects as well as future industrial applications will bring down the costs to manufacture nanophase materials and enhance the importance of nanomaterials in energy storage systems. Inorganic and organic nanocomposites (hybrids) are also great contenders for the next generation battery or fuel cell systems which may offer optimum characteristics. From the use of nanomaterials, it is thus expected that the functional performance of the electrochemical systems will be improved tremendously.

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Structural integration of materials belongs to two or more functionally different materials in monolithic form. respectively. Materials science and technology is seen as one of the most important disciplines along with information technology and life science that will pave the way to technology in the newly 21st century. metallic or organic materials. 85 . intelligent materials. Even today. One way of classifying nanocomposites is by Newnham's classification of conventional composites (Newnham. 1. such as ceramic. iron age. and automotive parts. Recent trends of materials research approach two aspects: compositional refinement and structural integration of existing materials. A composite is one or more distinctive components dispersed in a continuous matrix creating a compositional heterogeneity of the final solid structure. where the first number refers to the connectivity of one phase and the second to the connectivity of another phase. The continuous matrices can be ceramic. for instance. bronze age. Another classification of composite materials is based on the continuous matrix composition. The knowledge and technology of materials have been accumulated that most demands of industry can be met.12. Previously. is in the nanometer range. or Gibbsian solid phase. Nanocomposites 12. a great deal of effort worldwide has being directed toward developing new materials. In the 3-1 composite.. one dimensions. Each phase has zero.1 Introduction Materials research is so important that the historical ages of human civilizations have been named after the materials that enabled that age (stone age. two-.1 Classification of two-phases composite based on connectivity. or three-dimensional connectivity to itself. and three dimensions. 0–2. "Nanocomposite" is defined as a composite in which the distinctive component. one-. such as functional gradient materials. either in bulk form or as thin films. the information age is based on silicon-based semiconducting materials.1. The numerals 0. 2 and 3 mean that this phase connects by itself at zero dimensions. Arrows are used to indicate the connected directions. This classification is convenient for recognizing the structural relationship of constitutional phases. He has proposed a classification for a two-component composite by the numbers 0–1. two dimensions. Figure 12. The views are related by 90° counterclockwise rotation about z. or smart structures. 1–3. etc to describe the connective relationship of the component phases in the composites as shown in Fig. metallic or polymeric matrix. most elemental materials have been studied thoroughly and many single-phase materials have been successfully manufactured. the shaded phase is three-dimensional connected. Accordingly. large containers. A typical conventional composite is glass-fiber-reinforced plastic (GFRP) that is widely used in aircrafts. et al. and it is also applied to nanocomposites. etc). Two views of the 3-3 and 3-2 patterns are given because the two interpenetrating networks are difficult to visualize on paper. 12. The accepted length for the nanophase is less than 100 nm in at least one dimension. 1978).

n = 0 and n = -1. The simplest change of a composite property. the property of a fiber-reinforced composite can be evaluated by the following three equations. which is represented by the following equation (Kakawa. of the added components. Most of the property changes can be estimated by some rule of mixtures. respectively. Vi. 1990): Pi is the added component property and n is an experimental parameter (1 n -1). is monotonically increasing or decreasing with the increase of volume fraction. In the case of n = 1. The volume fraction of reinforcing fiber is Vf: 86 .Composites are expected to exhibit superior properties or better performance than their elemental or monolithic counterparts. assuming the properties of fiber and matrix are Pf and Pm. Pc.

(12. For example.Using a fiber reinforced plastic composite.4).1). the strength parallel to the fiber direction mostly follows Eq. and the nonlinear effects of property/performance improvement have been verified in some systems.4). e.g.2 Plot of change in property with constituent volume based on rule-of-mixtures.. In this case. 87 . Figure 12. 1990). 12.2). These equations are illustrated in Fig. Many nanocomposites have been experimentally investigated. emphasizing a high percentage of the atoms associated with the disrupted bonding of the grain boundary.3). which shows that Eq. up to 20 vol% in 20 nm materials (Fig. 12.2. In nanoparticles and bulk nanocrystalline materials. electromagnetic properties. Each crystalline particle consists of inner ordered lattice atoms and outer disordered grain boundary atoms (Fig. but a nanocomposite composed of Al2O3 and SiC shows 1500 MPa strength (Niihara and Nakahira. mechanical properties. (12. the strengths of Al2O3 and SiC are 800 MPa and 500 MPa. grain boundary interaction plays an important role in the strength improvement. and optoelectronic properties. (12. for example. and the electronic conductivity perpendicular to the fiber direction follows Eq. which cause some unusual electromagnetic behaviors that would not be expected from Eq. Nanocomposites differ from their conventional composites in the strong interaction of grains around grain boundaries. This is based on the occurrence of minimal chemical interaction between phases and lesser structural defects or flaws.2) gives the highest value of property of composites.3 Two kinds of atoms existing in the bulk nanomaterials. (12. the grain boundary atoms have a volume fraction much higher than conventional materials. These grain boundary atoms are electrically unsaturated and chemically active. These may be nonlinear changes or a rule of products. Figure 12. 12.

which show the increased interest in nanocomposites. we found 261 papers using the SCI database and 150 using EI database.4 Ratio of unsaturated atoms in nanomaterials. Scientists are increasingly researching nanocomposites. Figure 12.5).5 Literature search on nanocomposites using SCI and EI databases. A recent literature search showed that in the last seven years research articles number n on nanocomposites published in each year have increased approximately 25% each year and to total of 10 times. showing rapid increase of the number of the scientific articles published in the recent years.Figure 12. 12. In 1998. from 1992 to 1998 (Fig. 88 .

This chapter will review the processing and properties of nanocomposites with ceramic. 89 . and optical properties. optical properties were given more attention by researchers. and catalysis. in contrast to the SCI papers that showed focus on mechanical properties. Figure 12. metallic and organic matrices. followed by magnetic properties. and will summarize the general features. Half of the EI database indexed researchers mainly focus on mechanical property improvements. quantum dots. magnetic properties. electrical properties. magnetic properties. The mechanical properties.6 shows that the ratio of the top six properties of interest in nanocomposites. The greatest is mechanical properties.Figure 12. optical properties.6 The ratio of the major topics of interest on nanocomposites.

are 200–600 nm. electromagnetic wave. the large grain boundary effect. a red blood cell or a bacteria cell.2. the grain boundary volume fraction increases approximately 10 times in materials with a particle size of several nanometers compared to those with a particle size of a 100 nm. and the quantum confining effect. Assuming a grain boundary thickness of 1 nm. When the particle sizes in composite materials approach lengths of physical interaction with energy. (1) Small size effect A nanophase is defined as a particle or cluster with a size of approximately 100 nm. Cells. The big difference between nanomaterials and micrograined materials is the larger volume fraction of grain boundary atoms. as shown below: 90 . which results in unusual properties. Many natural basic units have this range of size. A magnetic domain is several tens of nanometers. A magnetic nanoparticle usually only contains a single magnetic domain whose domain wall is easy to move and polarize under electromagnetic field. Most of the unique magnetic and optical behaviors of nanocomposites are attributed to the small size effect. the periodic boundary conditions of the coupling interaction with the energy would behave different from its microscopic counterparts. which is a function of diameter (D) of the nanograin. or thermal conductivity. Optical wavelengths are several hundreds of nanometers.1 Physical Sensitivity: Three Effects of Nanoparticles on Material Properties Nanoparticles and nanoclusters may exhibit unique behaviors due to three effects: the small size effect. An atom on the grain boundary is unsaturated in chemical bonding and partially disordered in the lattice.12.2 General Features of Nanocomposites Nanocomposites differ from traditional composites in the smaller size of the component phases. 12. such as a light wave. The number of atoms on the boundary (ns) related to the total number of atoms in the grain (N) and is represented as the fraction of surface atoms F. The small size of the phases may cause stronger physical sensitivity of bulk materials to physical or mechanical energy and higher chemical reactivity of grain boundaries. (2) Grain boundary effect A crystalline particle is composed of two parts: the inner regular crystalline structure and the outer irregular crystalline structure at the grain boundary.

They utilized this solid state epitaxy to explain virtually all their observations of enhanced chemical reactivity. their processing is still very difficult. some metallic nanoparticles can burn when exposed in air. such as that shown in Table 12. These new energy levels give rise to the modification of optoelectronic properties such as spectral "blue shift" light emitting diode (LED). such as a nanoparticle.2 Chemical Reactivity Nanoparticles exhibit high reactivity during synthesis and processing of composites and in service situations.2. Although quantum dot devices are highly attractive for optoelectronics applications. This refinement-enhanced reactivity is an important factor for property improvements in nanocomposites. 12. are determined by quantum "confinement" effects. Lowering melting points of metallic nanomaterials and the electrical resistance change and optical behavior in metallic and ceramic nanomaterials may be attributed to the much higher activity of unsaturated atoms in nanomaterials. 1993) confirmed that nanocomposites have much higher reactivity than equivalent microcomposites and emphasized that solid state epitaxy is taking place in nanocomposites while they are heat-treated. some obviously metastable but very useful (S) Can crystallize glasses never crystallized before (S) Can radically refine the microstructure (S & C) Can tailor morphology (C) Can achieve properties (such as hygroscopicity) greater than components (C) The high reactivity of nanomaterials may enhance the interaction of the nanophase with the matrix and may exhibit the following results: 91 . At room temperature. Table 12.1. and some inorganic nanoparticles exhibit much higher adsorption of gas due to the enhanced reactivity.Such a huge quantity of unsaturated surface atoms will significantly enhance the reactivity of nanomaterials. Roy and co-workers (Roy. (3) Quantum confinement effect When electrons are confined to a small domain. the electrons behave like "particles in a box" and their resulting new energy levels.1 Reactivity achievements with nanocomposites: compositional (C) and structural (S) All reaction and sintering temperatures lowered by 150–300°C (C & S) Can drive complex ceramics to different final phase. At elevated temperatures. the activity of the nanoparticles significantly enhances the sintering process and lowers the sintering temperature by 200 degrees for alumina.

2. Assembly: nanoparticles are easy to aggregate and assemble in lines or other regular features in liquid or gaseous media. ZnO instead of carbon black. Decrease the electrostatic properties by adding TiO2. 3. They can be compact bulk materials. Ceramic matrix nanocomposites 1. passivation. 7. 5. heat retardation.2. Regrowth: nanomaterials are probably easier to recrystallize and regrow in processing and service conditions than traditional materials. and abrasion by refining particle size. Fe2 O3. Increase absorption of ultraviolet wavelength. 3. Sub-graining: nanoparticles enveloped into larger particles act as dispersed pinholes to divide the large particles into several parts. superplasticity by nanophases. 5. Increase in strength. Passivation of quantum dots. 3. metallic and organic materials. Some nanophase and matrix systems include mechanically hard crystallites of SiC in high strength ceramic materials. Metallic matrix nanocomposites 1. Matrices for nanocomposites can be ceramic. 12. and modulus. and delaminated clay minerals as filler in polymers. Enhance ductility. thin films. 6. Change electrical conduction and magnetic properties by increasing the disordered grain boundary interface. 2.3 Promising Improvements in Nanocomposites Nanocomposites are usually materials in which nanoparticles are dispersed in a continuous matrix. Epitaxial growth: epitaxy expanding and regrowth of the crystallites are confirmed in the nanomaterials. conducting particles of Ag in quantum confinement materials. 2. magnetic metallic phases of Fe and Co in magnetic materials. Matrices play the roles of structural stability. 4. 92 . Cr2 O3. formability. Increase the solubility for solid solution. 3.1. Increased nonstoichiometric phases: nanomaterials easily form chemically unsaturated bonds and nonstoichiometric compounds. Expected nanocomposites are listed below: 1. Increase the hardness and strength. Possible property Improvements differ for each matrix. 4. insulated ceramic SiO2 particles in luminescent materials. 2. 3. Use fine filler in organic materials to increase properties such as abrasion. transformation toughened ZrO2 in superplastic ceramics. Provide magnetic fluid by adding magnetic nanoparticles in fluid polymers. or mesoporous host-guest preforms. Rotation and orientation: crystallographic rotation and orientation of nanoparticles have been found in processing of nanocomposites. Polymeric matrix nanocomposites 1. Higher gas absorption: large specific area of nanomaterials can easily absorb gaseous species. hardness. and supporting substrates. 4. Increase the electrical resistivity by increasing the disordered grain boundary area. toughness. 2. Lower the melting point.

consolidation dramatically reduces the nanophases due to their surficial activity while the nanophases were explored at elevated temperature. But in the most cases. The whole process flow to prepare a nanocomposite includes powder preparation stage. Increase unique magnetic resistance by adding magnetic particles such as Fe. spinodal discomposition and phase separation. 2000). consolidation stage and annealing stage. part of the nanocomposites was formed in thin film by coating technology based on the chemical vapor deposition (CVD) and physical vapor deposition (PVD) in literatures. 5. Add semiconducting particles in mesoporous silica to absorb light and microwave radiation. An annealing and heat treatment after consolidation and sintering may produce nanophases by combining the eutectic crystallization. 5. which shall be introduced in detail in an other chapters. In general. 4..7. The most important improvements by nanophases are: 4. mixing stage.The applications of nanocomposites on semiconducting properties and magnetic properties have been studied in detail for the above matrices due to their practical usage. Cu.8 shows an example of Ti-N-C nanophases in the Si3 N4 grain due to the reaction of the added TiC micrometer particles with the matrix Si3 N4 grains at the sintering temperature (1820°C for 90 min). The most important stages of nanophase formation are in power preparation stages according to a literature search. Zr) N in which the TiN and ZrN separated in nanometer layers (approximately 30 nm in thickness for one layer) after the micrometer particles of the (Ti. and Au.9 shows a nanometer structure of (Ti. 2. leading to superparamagnetic behavior. Increase blue shift of optical spectra by adding nanoparticles in the polymer to form quantum dots.2. Semiconducting nanocomposites 1. and Ni in metals such as Ag. 93 . Zr) N solid solution were annealed at 1400–1600°C in N2 atmosphere (Li. 12. Mixing stage produces nanophases by mechanical alloying based on powerful ball-milling technology. Consolidation stage sometimes produces nanophases by the reaction of additive with matrix and the re-crystallization of the glassy phases. Figure 12. every stage can produce nanophases such as shown in Fig.7 Schematic showing the origin and generation time of nanophases in the nanocomposite synthesis process.4 Origin of Nanophases and Generating Stages A typical argument against nanocomposites is their instability and tendency to grow to micrometer size in the synthesis process. Figure 12. Magnetic nanocomposites Lower critical grain size to decrease in coercivity. The aerogels process. 3. Increase dielectric constant by adding metal Ag nanoparticles in epoxy resin. Except for the bulk nanocomposites. 12. coprecipitation and decomposition of polymeric precursor are frequently reported as brief processes to prepare the nanoparticles for the nanocomposites. Add semiconducting particles in the polymer to shield the electrostatic field. Most of the nanometer particles of an alumina powder tend to grow into micrometer grains when sintered above 1650°C. Figure 12. et al. Co.

8 Ti(N.Figure 12.9 Nanolayers formed in the (Ti. Figure 12. A: Si3N4 grains in the TiC/Si3N4 composite. B: Ti(N. B: Fracture surface of TiN grains showing the fracture steps. A: Natural surface of TiN grain with nanometer layers. C) nanophases in the Si3N4 grains after TiC/Si3N4 composite was sintered at 1820°C /90 min. Zr)N grains in TiN/ZrO2 composite after annealing at 1600°C in N2 for 2 h. 94 . C) nanophases in the Si3N4 grains.

et al. 95 . Based on the position of the nanophase particles in the final dense material.12. and nano/nano type as illustrated in Fig.10 (Niihara. 12. 1993). inter-type. Niihara classifies ceramic nanocomposites into four types: intra-type.. intra-type is expected to exhibit improvement on mechanical properties. intra/inter type.3 Ceramic-Based Nanocomposites Ceramic-based nanocomposites are composites that contain ceramic nanophases either comprising over half of the total volume fraction or with an interconnective relationship. Figure 12.10 Niihara's classification of ceramic nanocomposites based on the position of the nanophase: of the four types of nanocomposites. He emphasizes that the intra-type is mostly expected to improve the mechanical properties of ceramic matrix composites.

A mesoporous ceramic matrix is a common support or substrate for optoluminescent nanomaterials. Table 12. This section focuses on mechanical improvement of ceramic-based nanocomposites. The fracture surface showed transgranular fracture. 12. Although several groups have tried to reproduce this result.25 to 4.3. researchers have attempted to produce most ceramic material systems in the past 10 years.It has been investigated and confirmed in many compositional systems that ceramic nanocomposites for structural materials application exhibit great improvements in mechanical properties such as strength. Ceramic matrices are also used as stabilizers or passive hosts for some functional nanoparticles such as Al2O3 for Au quantum dots. A detailed observation of microstructure revealed that SiC nanoparticles were partially enveloped into large Al2O3 matrix grains and divided the matrix grains into several areas by forming subgrain boundaries inside the matrix grains. and SnO2 for Pt nanocatalyst. so far none has reached such high magnitudes of improvement as Niihara's group did.1 Strength Improvement of Ceramic-Based Nanocomposites Since Niihara's research group reported great improvement in the mechanical properties of ceramic nanocomposites (Niihara. 1991). and the crack deflected around the nanoparticles. They also revealed that the post-processing of heat treatment at 1350°C for 2 h of a sintered ceramic body can further improve the strength of SiC/Al2O3 up to 1500 MPa. toughness and hardness. the most impressive result is the nanosized SiC particle reinforced Al2O3 matrix composites in which the addition of 5 vol% SiC particles can increase the strength of hot-pressed Al2O3 from 350 MPa to over 1 GPa and fracture toughness from 3. The mechanism of annealing enhancement was conjectured to be attributed to either or both the microcrack-healing and microstress-removing at heat treatment temperature.7 MPa m1/2. 96 . SiO2 for Fe magnetic nanoparticles.2 shows typical results of Niihara's group on ceramic nanocomposites. Of these.

5 Nanocomposites 1520 850 700 1550 3. (Niihara and Nakahira. sub-grain formation and residual stress recontribution. flaw reduction. Mathematically.5 1. et al. 1994).5 7.2 4. Strengthening from reduction of flaw size Ceramic materials are flaw sensitive. but with the addition of 5vol% SiC the grains grew to less than 500 nm. 2. 1.8 4.5 3. The addition of a small amount of inert nanoparticles such as SiC would block the regrowth process due to the reduction of the diffusion of the constituents.5 The promising increase in strength is the greatest benefit of ceramic nanocomposites. Al2O3 grains originally 200 nm grew to over 1000 nm after sintering.7 4. The mechanism of strengthening is probably due to one or several of the following factors depending on the composition and microstructure: grain refinement. if the added nanophase reduces the grain size to half of the monolithic one. The Hall-Petch equation shows the simple relationship between fracture strength (σ) and grain size (d-1/2) assuming other factors remain unchanged (Borsa. regrowth. It can be understood from the above equation that refinement and size reduction of matrix particles (d) may increase the strength (σ) of ceramic materials.2 Some typical systems of ceramic/ceramic nanocomposites showing the mechanical improvements of nanosized SiC particles over micrometer sized SiC and Si3N4 Toughness (MPa · m1/2) System Microcomposites SiC/Al2O3 Si3N4/Al2O3 SiC/MgO SiC/Si3N4 Strength (MPa) Microcomposites 350 350 340 850 Nanocomposites 4.Table 12. while they are consolidated at elevated temperature. Strengthening from grain refinement The strength of ceramic materials is dependent on the grain size of the component phases. 1990). the strength could increase by approximate 40%. The improvement of strength varies from several percent up to three times that of the monolithic counterparts.. Ceramic matrix grains may increase in size. The relationship between the fracture strength (σf) of ceramic materials and the critical flaw size can be evaluated by the well-established Griffith equation: 97 .

and decrease in flaw size can lead to improvement in strength. 1996). Strengthening from sub-graining Very small particles can be enveloped into large matrix grains during the regrowth process at the sintering temperature. ν2 and E1. Strengthening from residual stress redistribution The second phase introduces a perturbation into the matrix by introducing a stress field. P. These small particles can then divide the matrix grain into several sub-grains due to the thermal mismatch. This sub-graining effect causes transgranular fracture and thus improves the strength. the thermal expansion coefficient mismatch (TECM. is equal to where Δ T is the cooling range during which plasticity is negligible and ν1. 3. x.α2) induces a hydrostatic stress in both the matrix and the second phase. K1c. (12. r. Nanophases added to ceramic materials sometimes produce a toughening effect. This equation indicates that increase in fracture toughness.8). While the ceramic composite is cooling from the sintering temperature. Y is a geometric factor approximately equal to 1. therefore. Δα = α1 . with the following relationship: 98 . The magnitude of this residual stress. E2 are Poisson's ratios and Young's moduli of the matrix and the particles.where K1c is a material's resistance to inherent flaws that is usually called the fracture toughness for brittle materials. The refinement of grain size leads to the reduction of flaw size and. and α is the length of the flaw. respectively (Fantozzi and Olagnon. It is clear that increased toughness by nanophases should lead to increased strength according to Eq. The magnitude of residual stress also depends on the distance. to an increase in the strength compared to equivalent monolithic materials. The critical flaw size in ceramic materials is in most cases proportional to the grain size. The mechanism for this effect will be discussed later. Ts. 4. from a point in the matrix to the particle and the particle's radius.

such as grain rotation to form the small angle boundaries with matrix grain and formation of solid solution within the grain boundary. In ceramic nanocomposites. The typical processing of ceramic nanocomposites is shown in Fig. The critical sizes for SiC particles are estimated to be 30–100 nm and 100–300 nm for matrices of Al2O3 and Si3N4. Nanoparticles. Consolidation of nanoceramic 99 . it can cause microcracking and result in a decrease in strength. SiC can absorb a small amount of Al2O3 at the sintering temperature to form a limited solid solution. The critical size and the critical amount of nanophase addition are important factors to induce the proper compressive stress toward the grain boundaries where cracks that propagate into the compression field would be deflected to regions of tension and result in improved strength and toughness.12 (Niihara. A reasonable magnitude of residual stress stored in the matrix will absorb elastic energy and contribute to a fracture energy increase. and greater than 5 wt% causes the entire Al2O3 matrix to experience tension. the moduli. based on 5 vol%—15 vol% addition. Sternitzke (Sternikze. can be introduced into the matrix by fine powders or pyrolysis of silicon-containing organic polymer (precursor). respectively.. et al. of the matrix. (1994) have experimentally measured the residual stress of SiC/Al2O3 using X-ray diffraction and found that a 5 wt% addition of nanophase is the critical amount for SiC/Al2O3.It is clear that a composition system with a large TECM and large grain size induces a large residual stress. This explains why most of the effective strengthening results for the SiC/Al2O3 system have been reported with less than 10 wt% addition. 1993). Levin et al. In contrast. and the applied pressure. Less than 5 wt% of SiC nanophase causes part of the Al2O3 matrix to experience compression. He concluded that SiC particles within the Al2O3 grain located close to grain boundaries strengthen the grain boundaries due to radial compressive stress and thus exhibit a strengthening effect. 12. Al2O3 and Si3N4 matrices have been greatly studied for the past decade. such as SiC. but the grain boundaries between grains of SiC and Al2O3 are almost clear or glassy. 1997) has tried to calculate the stress field distribution around a SiC particle in Al2O3 matrix and found that in a cubic-body-centered arrangement of nine equivalent particles the central particle results in a high tensile stress and the other particles 100 nm away from it generate compressive stresses up to 120 MPa. The nanophase for these matrices is SiC nanoparticles. SiC nanoparticles within Si3N4 matrix exhibit more reaction and interaction with matrix grain. but if the residual stress is too large. The critical size of the second phase that will not cause microcracking in the matrix has been given by Davidge and Greene (1968): This equation means the critical size of the second phase which causes the microcracking is dependent on the surface energy.11 and the typical result is indexed in Fig. 12. γs. A second phase smaller than this critical size can absorb the external energy and raise the strength.

100 .12 Typical improvement on properties of ceramic nanocomposites. Figure 12.11 Flowchart of preparation processing of a typical ceramic nanocomposite. Figure 12. Annealing process was effective.composites is usually conducted by hot-pressing sintering but pressureless sintering is also useful for the alumina matrix.

101 . nanophases toughen only by phase transformation and microcracking. transformation toughening. microcracking. 12. ZrO2/mullite. TiC/Al2O3. though a number of experiments have been conducted by independent researchers for the last decade. TiC/Si3N4. A few researchers reported the increase of fracture energy in nanocomposites using the indentation method (Kodama and Miyoshi. ZrO2/Al2O3. TiN/Al2O3. Nanophase and fine particles of tetragonal ZrO2 greatly improve the toughness of bulk ceramic and other brittle materials.Other systems that have been studied include SiC/mullite. It is believed that the addition of an inert stable nanophase would improve the toughness of brittle materials by the microcracking mechanism.3. However. Expansion of the volume of the t-ZrO2→m-ZrO2 transformation counteracts the crack tip and tends to close the tip opening. Experimental verification of the toughening effect of nanophase particles in brittle materials requires further study.2 Toughening Effect of Nanoceramic Composites There are a few approaches to improve the toughness of brittle materials: crack deflection. and crack bridging. and BN/AlN. The improved toughness for Al2O3 and Si3N4 may be higher than 3 to 6 MPa · m1/2. This transformation may be induced by any stress such as the machining force in the surface and the crack tip opening force (crack stress field) inside the materials. The crack tip stress induces the transformation of t-ZrO2 when the crack has propagated to the face of t-ZrO2 grain. The toughening effect results from the transformation of ZrO2 from the tetragonal phase to the monoclinic phase. TiO2/Al2O3. which results in an apparent increase of the toughness. Most of them have been confirmed to exhibit improvements of strength and toughness. 1990) but direct improvement of toughness of significant magnitude has not been reported so far. SiC/MgO. resulting in volume expansion of approximately 5%.

3 Improvements of Nanoceramic Composites on Hardness and Wear S. A nanophase may toughen the matrix by influencing the morphology of the matrix grain and thus the microstructure of the bulk materials. They also found that when the particle diameter decreased from 70 nm to 2. 12. (1989. The presence of the nanophase may restrict the growth of most matrix grains and cause some abnormal grain growth in some systems. There must exist a proper amount of nanophase to balance between oppressing the growth of most matrix grains and enhancing elongation of other grains. as shown in Fig. Figure 12. 102 . have prepared thin films of the nanoparticles of TiN and W2N mixed into α-Si3N4 deposited by plasma CVD on 500–550°C substrate and found the hardness exceeded 50 GPa. 12. Further composition selection and microstructure design associated with synthesis and processing are still needed to demonstrate the toughening effect of nanophase in nanocomposites. and the highest plastic hardness of nanometer TiN reinforced silicon nitride composite is close to that of diamond. Niihara et al.13. (1996). The elongated grain may act as a reinforcement to significantly improve the toughness similar to a short fiber or whisker.5 nm. 1988) reported that a small amount (less than 10 vol%) of SiC particles with diameters of less than 100 nm can enhance the development of an elongated Si3N4 grain.13 Hardness increases with the decreasing dispersed nanoparticle size. Veprek et al.3.Another possible way for nanophases to toughen ceramic materials is from morphology control. the plastic hardness approached that of diamond.

which is an improvement of over 200%. Db is the diffusion constant in grain boundaries and T is the temperature. A common expression for wear resistance is the volume of the materials removed (V) as a function of applied load P. wear plates. changing the grain size from 10 µm to 10 nm would increase the creep rate by nine orders of magnitude assuming all else remain constant. A is a constant.2 nm/s in the monolithic material to 1. 103 . Most deformation and creep are related to grain boundary diffusion.4 nm/s in the nanocomposite.Wear resistance is an important property for alumina materials when used as cutting tools. and transportation support plates. Nanomaterials and nanocomposites with large quantity of grain boundaries will exhibit a greater creep rate. ξ is the grain boundary width.3. as shown in the following: One can understand from this equation that increases of either toughness or hardness or both in alumina will improve its wear resistance. 12. (1987) indicated the possibility for brittle materials to have ductile deformation at low temperature when the grain size is on the order of 100 nm or less. He also found that the wear rate is proportional to the grain size (µm) when the grain size is smaller than 2 µm. It also has the potential to enhance the formability of ceramic materials. can enhance the boundary diffusivity. Anya (1998) has studied the effect of SiC nanophase dispersed into Al2O3 on wet wear resistance. Karch. 1963): where dε/dt is the strain rate. Superplasticity along with the refinement of grain size is desirable in ceramic materials. furthermore. Ω is the atomic volume. The grain refinement. thereby. which may even lead to superplasticity. He found that 10%—15% addition of SiC nanophase in alumina decreased the wear rate from 3. by decreasing d3 and increasing Db. A well-known relation in this respect is the Coble creep equation (Coble. the hardness H and fracture toughness K of materials. For instance. et al. σ is the stress. increasing the wear resistance. k is Boltzmann's constant.4 Superplasticity of Ceramic Nanocomposites Refinement of grain in crystalline materials also affects the creep behavior since one of the predominant mechanisms for creep involves atomic transport along the grain boundaries. This equation shows that the reduction in grain size may cause a considerable increase of the creep rate. It has become a new challenge to change the fracture behavior of ceramic materials from brittle into ductile. The explanation of the wear resistance improvement of the nanocomposite is that nanophases induce compressive stress toward the grain boundary and enhance the bonding strength of the boundaries.

are common candidates for the 104 . Ni. 3.3.14 A plastically forged ceramic component fabricated from a nanostructured preform ring. Wakei et al. Weertman and Averback (1989) have summarized the common characteristics of superplastic materials: 1. Ti. showing the effect of nanosized SiC on reduction of creep and strain.6 Ceramic-Based Nanometallic Composites Ductile metallic nanoparticles usually exhibit obvious strengthening effects in a ceramic matrix. small grain size to make diffusion easier. Figure 12. 12. with melting points 1825°C and 1675°C. 2. high energy grain boundaries to enhance diffusion. (Edelstein and Cammarata.5 Improvement of Nanoceramic Composites on Creep Thompson et al.Karch. equiaxed grains to reduce the sliding resistance of grain boundaries. Mo. Co. (1997) report that the addition of 15 vol% SiC nanoparticles to Al2O3 was sufficient to reduce the tensile creep rate by two to three orders of magnitude. Cr and their alloys. This component was plastically forged from a preform ring of nanophase ZrO2 ceramic at 1400°C in less than 15 min. Figure 12. The forging operation was performed at 1400°C in less than 15 min. High temperature metals. presence of second phase to restrict grain growth. such as W. 1996). (1986) demonstrated that yttria stabilized tetragonal zirconia polycrystals (Y-TZP) with approximate 300 nm grain size could be elongated over 100% in tension. respectively). (1987) have reported that nanophase TiO2 and CaF2 exhibit extensive ductility at room temperature (tested at 80°C and 180°C. et al.14 shows an example of a prototypical forged preform (PFP) net-shaped part.3. Utilizing superplasticity has made it possible to forge and machine a prototypical part made of hard brittle ceramic materials into a net-shaped part at low temperature. 12. 4.

V. the domain walls are easy to move.5 3. Improved magnetic properties such as coercivity. D. Krstic has summarized Al2O3-based nanoparticle composites in Table 12. Increased hardness.2 4. 12. 2.0 µm grains size alumina increased the strength to 1000 MPa from 500 MPa and the magnetization changed up to 6% in comparison with micrograined composites. 1998).3 Nanocomposite 1105 920 1090 816 3.5 4.4 Metallic-Based Nanocomposites Metallic-based nanocomposites are expected to have advantageous mechanical and magnetic properties. resulting in better 105 . 4. saturation magnetization and magnetocolatic properties.5–1. They attribute this improvement in strength to refinement of the matrix grains and saturation magnetization to magnetic nanoparticles. Increased miscibility of the non-equilibrium components in alloying and solid solution.dispersoids. (1998) reported that the ductile metallic nanoparticles of Ni-Co alloy not only improved the strength but also introduced a stress sensing function to the alumina material by detecting its magnetic property via the applied stress. 5. Addition of 10 wt% Ni-Co alloy of 100–200 nm grain size dispersant into 0.5 Awano (1997) and Oh et al. and the exchange coupling is substantially enhanced in the magnetic field.5 3. The promising improvements of nanocomposites over traditional composites are: 1. When the sizes of the magnetic particles are small enough to approximate the size of a single magnetic domain. strength and superplasticity.5 3. Lowered melting point.0 7. Increased electrical resistivity due to increased disordered grain surfaces. 3.3 (Krstic. The most attractive challenges of metallic nanocomposites are the unique magnetic properties. their magnetic spins are all aligned to produce a magnetic moment in one direction. superpara-magnetization. Table 12.3 Room temperature fracture toughness and strength of metal nanoparticle reinforced Al2O3 matrix nanocomposites in comparison with micrometer sized composites (metal/ceramic matrix) Toughness (MPa · m1/2) System Microcomposite W/Al2O3 Mo/Al2O3 Ni/Al2O3 Ti/Al2O3 Strength (MPa) Microcomposite 350 350 350 350 Nanocomposite 4. This data shows that the strengthening is approximately three times the microparticle reinforced composite.

Nanometer sized materials of immiscible metals have been deposited. 1992). The critical sizes vary a little depending on the component elements. The mechanism is alignment of the ferromagnetic domain by the magnetic field reducing the scattering of the electrons and thereby decreasing the electrical resistance. keys. GMR is the phenomenon of a large decrease in electrical resistivity of certain materials when exposed to a magnetic field.5 Polymer-Based Nanocomposites 106 . magnetic recording heads and microwave applications. a desirable coercivity can be obtained. increase electrical resistance and increase catalytic activity. and tickets) and low coercivity for power transformers. It is known that a smaller particle size results in a larger GMR effect. Possible applications are magnetic sensors and new storage devices. It is known that a maximum value for coercivity exists in nanocomposites containing magnetic crystallites of an optimum size to a single magnetic domain. Ag. such as the micromotor. Nanocrystallite size larger or smaller than the optimum size leads to a sharp decrease in magnetization. It has been found that Cr nanoparticles align in chains and the particles grow in perfect morphology and with the same crystal habit plane. Giant magnetoresistance (GMR) effect is another attractive property of the magnetic nanocomposite. array and mesoporous materials. This effect is mostly exhibited in magnetic multilayered nanocomposites (such as Fe/Cr multilayered nanocomposite) and was recently found in magnetic/conductive nanocomposites containing magnetic nanoparticles such as Co. 12. et al. nanoparticles are easily moved and crystallographically rotated in viscous fluids and tend to self-assemble in chains. Iron powder with a crystallite size of 13 µm exhibited 900 Oe in comparison with 10 Oe on bulk Fe (Gangopadhyay. One of the well-known features of metallic nanomaterials is the lowered melting point due to the relative increase of the activity of the grain boundary and the unsaturated atom volume (El-shall and Edelstcin.magnetic properties. This method allows the in situ fabrication of metastable phases embedded in nanocomposite. By controlling the soft magnetic phase (α-Fe) or hard magnetic phase Nd2Fe14B (commonly named 2-14-1 phase) in nanometer size. Au.. and the metastable powder was annealed to cause the phase separation. Due to the relatively higher electrical attractivity to the nanoparticle's mass. The composition producing the highest GMR is commonly near the percolation threshold. Fe embedded in conducting metallic matrices of Cu. NdFeB ternary alloy is a common magnetic material but its intrinsic coercivity of less than 9 kOe limits its application in certain areas. The interfacial activity and grain boundary volume also affect the self-diffusion coefficient. Changing the size of the hard magnetic crystallite or the substitute composition can result in high coercivity that meets the requirements of high density recording materials (magnetic credit cards. Alumina and AlOOH also have self-assembling single chains. High density magnetic recording materials require a high coercivity and a high magnetization. Wide range solid solubility and alloying of immiscible metals have been observed in metallic nanocomposites. 1996).

light weight and low cost. The layers of aluminosilicate are approximately 1 nm in thickness and 1 µm in diameter. hardness. Montmorillonite can absorb 20 to 30 times its own volume in water. but the polymer intercalated into the layers can separate the layers into nanoplatelets (Kornmann. polypropylene. Their matrices may be epoxies. high-speed printing film. fire-retartant pouches. Organic nanocomposites have the advantages of common polymeric materials including high toughness. Conducting polymer-smectite clay thin films can demonstrate promise as active components in sensing devices because inorganic clay serves as a porous structural framework for polymeric sensing materials. A group of researchers have shown that nanoplatelets greatly improved modulus. They (1998) reported that only 1. thermal and barrier properties without significant loss of clarity. and shock absorbers. Recent approaches on clay-plastics composites are popularly focused on using the structurally separated monolayered clay or nanoplatelets in the plastics. as well as adding greater structural and thermal stability to the composite. During the 1990s. mechanical properties and flame-retardant. magnetic or conducting metals and oxide ceramics. Germany developed fused silica as a substitute for ultrafine carbon black particles used for rubber reinforcement when petroleum was needed for tanks. gasoline tanks and fuel-line tubes. Many metallic hydroxides and polymers are easy to insert into the layers to form intercalation. fluoropolymers and other plastics. There is an application of scratch-resistant polymers molded in color for interior and exterior parts of automobiles.5 vol% of delaminated montmorillonite enhanced the toughness (fracture energy) of unsaturated polyester from 70 J/m2 up to 138 J/m2. Normal intercalation will space the distances between the aluminosilicate layers to a certain degree. They reported the relative permeability of nanocomposite greatly decreased compared to the conventional composite. The promising improvements of the nanoparticles in polymeric matrices are expected to be in structural. It can absorb water or other polar ions between the layers and swell the interlayer distance many times similar to smectite. and strength without the loss of toughness and formability compared to conventional fillers for plastics and nylons. easy formability. 107 . and NASA in the United States developed a magnetic fluid in which nanometer sized magnetic particles of iron oxide are suspended in the fluid polymer. Commercial Nylon-clay hybrid with 2% clay can be used as a gas and UV barrier as well as for high heat resistance. Some unique optical and electrical properties can also be expected to appear in nanocomposites due to the size effect and high reactivity. The dispersed nanoparticles may be inorganic or clay fillers. good transparence. Giannelis (1998) reported that a doubling of the tensile modulus and strength is achieved for nylon-layered silicate nanocomposite with as little as 2 vol% of inorganic content and the heat release rate in the nanocomposite is reduced by up to 63%. Following are some typical applications: 1.Certain types of polymer nanocomposites have been produced commercially for more than half a century. Finer filler: Clay is a category of fine layer aluminosilicate mineral and is often used as the filler in the plastics. toughness or impact strength compared to common organic composites. food packages. the Japanese manufactured metallic nanoparticles for producing magnetic recording tapes. During World War II. 1998). et al. They can also be used in barrier packages. polyesters. Intercalation is an important technique to modify the layer materials.

6. 5. Oxide nanoparticles such as TiO2 and Cr2O3 can absorb and scatter UV radiation by dispersing them into polymer or pigment. 3. This nanocomposite is expected to have a switching application in electronics.2. Toughness improvement of nanoparticles in a ceramic matrix has been expected but the practical progression is still underway. (1998) investigated the magnetic properties of nanocomposite film in which γ-Fe2O3 nanoclusters were dispersed into optically transparent block copolymer and found a hysteresis with the saturated coercivity H oc equal to 530 Oe. Sohn et al. Metallic-based nanocomposites are mostly produced by mechanical alloying method (for structural application) and vapor-medium deposition method (for magnetic and related functional application). which has a promising application as UV protection film. One uses transparent/formable polymer as the passive matrix or substrate for optical materials. Nanoclusters are highly reactive and must be passivated by dispersion or confined in insulated matrices or hosts in the practical application. which is also color tunable as a function of applied voltage. protect the plastics against color degradation. and achievements in strength enhancement as well as hardness and wear resistance have been reached in ceramic-based nanocomposites including nanoceramic/ceramic composites and nanometallic/ceramic composites. Nanoceramic composites that exhibit good plasticity provide a promising technology to forge the hard ceramic materials into complicated forms. micelles. CdS nanoparticles have promise as photoluminescent properties. Gao et al. rendering the film conductance with linear current-voltage characteristics when the voltage is higher than a certain threshold value. 12.6 Summaries of Nanocomposites Most dense nanocomposites are studied with the intent of improving mechanical properties. (1993) prepared Au/polyethylene composites by orienting nanometer sized Au (60 nm) cylinder array on polyethylene polymer and observed the dependence of absorption maximum on the polarization angles of incident light in the composite where the absorption maximum shifts from 550 nm to longer wavelengths (800 nm) when the polarization angles of incident light with 330 nm wavelength are changed from the direction perpendicular to Au cylinder axes to parallel to the axes. membranes and anionic polymers. Colby et al. Further approaches to nanocomposites probably include assembling nanoparticles and embedding 108 . CdS/dendrimer nanocomposites that contain CdS nanoclusters of 2–4 nm show significant absorption as UV light. Improvements in magnetic properties have excelled in recent years. (1995) found that in the sandwiched structure of polymer layer-conducting nanoparticle layer-polymer layer the conductance increased by a fact or of 107. There are many kinds of matrices such as zeolites. porous glass. Mechanical property improvements of nanodispersoids are attributed to grain refinement and residual stress optimization. The other uses finer inorganic powders as fillers to improve the mechanical properties of matrices. Optical application: Semiconductor nanoclusters (referred to as quantum dots) possess chemical and physical properties that differ substantially from those of analogous bulk solid. Nanoparticles can be used as light emitting diodes (LED) with high conversion efficiency by using quantum dots embedded in polymers. or can be used for solar protection creams. Calvin (1994) assembled CdSe nanoparticles on the surface of electroluminescent polymer (PPV) and found green light emitting from the polymer and red light from the nanoparticle layer. 4. Dendrimer is a quasi-spherical organic polymer that has well-defined structures with less dense interiors and densely packed surfaces. Polymer-based nanocomposites are composed of two groups.

Sorensen. 354 (1994) Coble K. 12. E. Tech. Microscopy. 38.. I. J.. and T.. and Niihara (1993). (1998). 3. B. Q. Kostilas.. by. Material Science and Engineering ed. J. Berglund L.... 73. L. Olagnon. Papaefthymiou and A. Nanomaterials. JOM January 44 (1998) Borsa C.. 185 (1996) Gangopadhyay S. 997 (1997) Bhaduri S. M. Brook. J. J. Biringer and H. Cammarata. and R. Institute of Physics Publishing. Phys. R. 1679 (1963) Colby A. J. 177. 431 (1993) Davidge R. 330. 3081 (1990) Kornmann X. Bhaduri. Vac. Materials Science Forum.. V. 305 (1994) Calvin V. C. 556 (1987) Kodama H. MRS Proceedings. Hornyak Jr. J. The unique electric. 533 (1998) Awano M. R. 629 (1968) Edelstein A. Nanocomposites for functional materials: Bhaduri and Bhaduri (1998). J. Seramikkusu. A. L. R.. Ceram. Martin. References Anya C. Appl. 32. Sternitzke (1997). S. Edelstein A. B 13. Polymer Engineering and Science. Todd and R. Wu and S. Stockert and C. Nanomaterials. Appl. C. C. 209 (1998) 109 . and Kruis et al. 1351 (1998) Krstic V. C. Xue. magnetic and optical properties of nanocomposites will result in new applications in the coming years. J. Nanocomposites with improved mechanical properties: Krstic (1998). S. 374. Jiao. J... Materials Sci. Phys Rev. and S. L.. Am. A. D. Q. Nature. Dale. 9778 (1992) Gao H.. K. Tailoring Ceramic Composites (Japanese). S. Rittner and Abraham (1998). Green. J. Sterte. Agune Shyofusha Publishing (1990) 96 Karch J. 34 (1996) Fantozzi G. B 45. 675 (1998) Kakawa Y. 282–283. Klabunde. 577 (1996) El-shall M. P. Rigueiro et al. (1998). D. For more detail the following reviews are recommended: 1. F. 1242 (1995) Giannelis E.. 286. S. J. Soc. and C. Pang. G. 34. 24. Nature.. Hadjipanayis. Organometal Chem. and T. Z. Gleiter. W. Reimanis (1997). and J. ed..them into heteromatrices to form multiple dimension nanocomposites. Edelstein. Ceramics International.... 2. 11. Sci. and A. Miyoshi. S. B.

Nakahira. 182. Fissan and A. R. by V. Nakahira and Sekino T. 159 (1997) Rigueiro J. Nagoya. 216 (1998) Sternitzke M. Ellces. S. M. Eng. Acta Metall Mater. H. H. 242 (1993) Sohn B.. Ceram. 1. F. 13. Papaefthyniou... 974 (1991) Niihara K. Wieder.. Nakahira.. Mater. 511 (1998) Levin I. 46 (1996) Wakei F. Kaldan. J.. D. Niihara. 129 Niihara K. Hirabayashi. 3013 (1998) Reimanis I. Haussmann and Reiprich S. Aerosol Sci. Vac. T. H. E. E. Advanced Structrural Inorganic Composites. Abraham. M. A.... 81. Y. 525 (1978) Niihara K. Harmer and R.. Tech. Sando and K. Elsevier Publisher (1990) Niihara K. Sci. J. Cook. Sasaki and M. Materials Research Bull. J. Yanagida. 5399 (1998) Rittner M. by Sridhar Komarneri. eds. 405 (1993) Oh S. P.. Moya. Sakaguchi and Y. Nakahira. G. Cross. 567 (1997) Veprek S. T. Japan. A. 29. A. Tenmery. 78... January 36 (1998) Roy R. MRS Proceedings 286. Acta Mater. M.. Ceram Soc. JOM. N.. S. H. J. MRS proceedings (1989) 4. Matsuno.. 42. D. J. 15–17th March (2000) Newnham R. J. J. Cohen. ed. American Ceramic Society (1988) Niihara K. Llorca. E.. J Magn. 17. and L. Ceram.. Soc.. C. MRS Proceedings 286. H. 259 (1986) 110 . P. Skinner. Mater. Advanced Ceramic Materials. W.. E. by Vincenzizi P.. P. Peled. Chan. Miranza. Proceedings of the JFCC International workshop on Fine Ceramics 2000. P. 46. 1061 (1997) Thompson A. A237. Matsubara. M. D. et al. G. J. 1147 (1994) Li J. B. A14.. E. & Magn. Am. Proceedings of the Third International Symposium on Ceramic Materials and Components for Engines.. J. J. Soc. Am. Eur. Ceram. and A. and T. A.. Brandon.. Pastor. Sci. ed. M. Soc of JPN 99.Kruis F.

1996. significant progress has been made in controlling the growth of multi-walled carbon nanotubes (MWNTs) on surfaces using chemical vapor deposition (CVD) methods. A nanotube has high Young's modulus and tensile strength. suspended SWNT architectures with nanotubes directed towards well-defined orientations are synthesized. Dekker. 1996). 1991. The nanotubes are difficult to purify. Arc discharge (Iijima. et al. Wong. 1999). Yakobson and Smalley. et al. individual SWNTs are grown on specific sites on surfaces..1 Introduction Carbon nanotubes have attracted much attention in the past several years because of their unique and potentially useful structural. et al. 1999) and electron field emission sources (de Heer.. Ren. diameter. 1998. 1999) nano-electronic devices (Tans. et al. et al... 1998). as well as their atomic structures including helicity. and it remains unclear how to scale up nanotube production to the kilogram level using the evaporation approaches. 1995. This sets a limitation to the quantity of nanotubes that can be synthesized. 1996. However.. 1996. Recently. The second issue relates to the fact that evaporation methods grow nanotubes in highly tangled forms mixed with unwanted carbon or metal species. Martel. The results include MWNTs self-oriented perpendicular to substrates and assembled into regular arrays. The nanotube architectures derived by controlled chemical synthesis have opened new possibilities in fundamental characterizations and potential applications of novel nanowire materials. Pan. Utilization of these properties with individual or ensembles of nanotubes have led to advanced scanning probes (Dai. and can be metallic. Collins and Zettl. 1998.13.. et al. Developing controlled synthesis methods to obtain ordered carbon nanotube architectures is an important and viable route to fundamental characterizations and potential applications of nanotube based molecular wires. Bethune.. 1996) have been the principal methods for obtaining high quality nanotube materials. et al. Fan. et al. Ebbesen.. et al. the growth of single-walled nanotubes (SWNTs) into ordered architectures has been challenging. Long and well-aligned MWNTs on large-scale substrates have been synthesized (Li.. et al. 1997) and laser ablation (Thess. 1999). 1998. The ultimate goal in nanotube synthesis should be gaining control over the locations and orientations of nanotubes. et al. 1998a.. electrical and mechanical properties (Dresselhaus. Soh.. Iijima and Ichihashi.. 1998b... there are several key issues concerning both methods. and synthesizing nanotubes on rationally designed substrates containing patterned catalyst.. et al. Bonard. By enabling a CVD method for structurally perfect SWNTs. semiconducting or semimetallic depending on the helicity and diameter (Dresselhaus. 1996. The key approaches include understanding the chemistry of catalyst materials and nanotube growth. et al. 1998b.. single-walled nanotubes are true molecular wires with their diameters in such a regime (about 1–5 nm) that 111 . et al.. et al. et al. Wang. and topological defects. 1993.. et al. Also. Hafner. 1998. In particular. This chapter presents our recent development of controlled CVD synthesis strategies to obtain ordered multi-walled and single-walled nanotube structures. Nevertheless. 1993. et al. Saito. 1996. 1997. 1998. manipulate and assemble for building nanotube device structures. The first is that these methods involve evaporating carbon atoms from solid carbon sources at ≥3000°C. for the first time. et al. Journet. 1998. Growth and Properties of Single-Walled Nanotubes 13..

The first step in a CVD process involves the absorption and decomposition of hydrocarbon molecules on transition-metal (Fe. Single-walled nanotubes are shown as examples. Multi-walled or single-walled can be synthesized by CVD depending on the particle size. we will show that our growth strategy readily allows SWNTs to be integrated into electrical circuits and addressed individually..1 Schematic growth modes of carbon nanotubes in CVD. 13. Typically.1. The carried-along particle is responsible for supplying carbon feedstock needed for the nanotube growth.. right panel). Also. as well as the type of hydrocarbon feedstock and growth conditions. The typical growth temperature Tg is typically 500 °C ≤ Tg ≤ 1000 °C. 1990. Endo.1. Right panel: tip-growth mode. Figure 13. Tibbetts. Snyder. et al. 112 . Co. The carbon atoms diffuse into the interior of the catalyst to form a metal-carbon solid state solution (Baker. Ni. left panel). the catalytic metal nanoparticles are typically obtained on high surface area support materials such as Al2 O3 and SiO2. 13.1). Baker and Rodriguez.2. etc. 13. Left panel: base-growth mode. SWNTs serve as ideal systems to study physics problems in quasi one dimension. 1984). functional electronic structures based on individual SWNTs with comparable characteristics as conventional silicon devices are demonstrated. The base-growth mode involves the metal catalyst particle pinned on the support substrate. 1994). et al. Systematic electron transport measurements are carried out to elucidate the intrinsic electrical properties of various classes of nanotubes. 1988.1 Chemical Vapor Deposition Chemical vapor deposition of hydrocarbons over metal catalysts has been a classical method to produce various forms of carbon fibers. 13. To this end. 1989.the electronic structure of a SWNT sensitively depends on its chirality. and the nanotube lengthens with a particle-free closed end. For the synthesis of nanotubes. two modes of nanotube growth can operate in CVD. The tip-growth model involves a metal catalyst particle at a nanotube end being carried away as the nanotube lengthens (Fig.2 Synthetic Strategies for Various Nanotube Architectures 13. 1987. Subsequent precipitation of carbon from the supersaturated catalyst particle will then occur and lead to the formation of a carbon tube structure (Fig. Carbon feedstock is supplied from the base where the nanotube interfaces with the catalyst material (Fig. filaments and multi-walled nanotubes in the past (Tibbetts. Tibbetts.) catalytic particles. 1983. The size of the catalytic particles determines the size of the nanotubes. 1989.

1998a. previous methods have relied on growth of nanotubes in confined environments including the pores of mesoporous silica or channels of alumina membranes (Li. et al. Figure 13. et al. The substrates are porous silicon obtained by electrochemical etching of n-type silicon wafers in HF/methanol solutions.2(b). et al. Pan... 1992).. CVD growth using the substrate is then carried out in a 2 in. 13. 1999). Our synthesis approach involves catalyst patterning and rational design of the substrate to enhance catalyst-substrate interactions and control the catalyst particle size. tube furnace at 700°C under an ethylene flow of 1000 sccm/min for 15–60 min. We have found that nanotubes can self-assemble into aligned structures during CVD growth. Kyotani. we have developed a CVD approach to grow nearly perfect SWNTs by using methane as the carbon feedstock (Kong.Notably.2. and the driving force for self-alignment is the van der Waals interactions between nanotubes (Fan. et al. 1996). et al. The length of the nanotubes and thus the height of the 113 .2 Growth of Self-oriented Multi-walled Nanotubes In controlling the orientation of nanotubes during CVD growth. Only recently. a pitfall of CVD synthetic approaches has been that defective tubular carbon materials tend to be formed. 1996. inset) within each block are well aligned along the direction perpendicular to the substrate surface. This result will be presented later in the chapter. Che. The high resolution SEM image (Fig. 13.2(b)) reveals that the MWNTs (Fig.. 13. et al. The resulting substrate consists of a thin nanoporous layer (pore size 3 nm) on top of a macroporous layer (with submicron pores) (Vial and Derrien. 1998. Smith and Collins. 1998b). Patterned catalyst squares on the porous silicon substrate are obtained by evaporating a 5 nm thick iron film through a shadow mask.2(a) shows a scanning electron microscope (SEM) image of regularly spaced arrays of nanotube towers grown on top of patterned iron squares on a porous silicon substrate.. 1998. The nanotube towers exhibit very sharp edges and corners with no nanotubes branching away from the blocks.. 1994.

1988. filaments and MWNTs (Tibbetts.towers can be controlled in the range of 10–240 µm by varying the CVD reaction time. The porous silicon substrates exhibit important advantages over plain silicon substrates in the synthesis of self-aligned nanotubes. et al. 1989). Structurally perfect SWNTs can now be grown in a CVD process using methane as carbon feedstock and iron-oxide nanoparticles supported on high surface 114 . which allows the growth of nanotubes perpendicular to the substrate. 13.2. This result suggests that ethylene molecules can permeate through the macroporous silicon layer and thus efficiently feed the growth of inner and outer nanotubes within the towers. The nanotubes grown on porous silicon substrates exhibit monodispersed diameters since catalyst nanoparticles with a narrow size distribution can be formed on the porous supporting surface. 1983. Since the nanoporous layer on the porous silicon substrate serves as an excellent catalyst support. Figure 13. Growth on substrates containing both porous silicon and plain silicon portions find that nanotubes grow at a higher rate (in length/min) on porous silicon than on plain silicon. 1999). 1994.3 Enable the Growth of Single-Walled Nanotubes by CVD Chemical vapor deposition methods have been very successful in synthesizing carbon fibers. The inset shows a TEM image of the bundled MWNTs. CVD synthesis of high quality SWNTs is only recent. Endo.2 (a) Scanning electron microscopy image of arrays of bundled multi-Walled nanotube towers. The smallest self-oriented nanotube towers synthesized by our method are 2 µm × 2 µm wide. the outmost walls of nanotubes interact with their neighbors via van der Waals forces to form a rigid bundle. and the strong catalyst-support interactions prevent the catalyst particles from sintering at elevated temperatures during CVD growth. Snyder. However. Baker and Rodriguez. (b) A high resolution SEM showing aligned MWNTs within a tower.. 1990. the iron catalyst nanoparticles formed on the nanoporous layer interact strongly with the substrate and remain pinned on the surface. and the width of the towers is controlled by the size of the openings in the shallow mask.. et al. The mechanism of nanotube self-orientation involves the nanotube base-growth mode (Fan. During CVD growth.

1998a).. and obtain nearly defect-free tube structures. High temperature conditions (850–1000°C) are employed in the growth in order to overcome high strain energies in forming small diameter SWNTs (<5 nm). and retains these characteristics at high temperatures without sintering. we find that the chemical and textural properties of the catalyst materials dictate the yield and quality of SWNTs (Cassell. we have found that a good catalyst material for SWNT synthesis necessarily exhibits strong metal-support interactions.3 A TEM image of SWNTs synthesized in bulk using a catalyst supported on a sol-gel derived alumina-silica hybrid material.area alumina as the catalyst (Kong. possesses a high surface area and large pore volume. et al. Through systematic studies. We have found that methane is stable at elevated growth temperatures without appreciable self-pyrolysis. This stability prevents the formation of amorphous carbon that tends to cause catalyst poisoning and overcoating the nanotubes.. 1999b).3 is a transmission electron microscopy (TEM) image of SWNTs synthesized in bulk by using this catalyst. Cassell.. 1999b). Figure 13. Shown in Fig. Catalytic decomposition of methane by the transition-metal catalyst particles is thus the dominant process in SWNT growth (Kong. 1998a. The strong metal-support interactions allow high metal dispersion and thus a high density of catalytic sites. The open pore structure of a catalyst allows efficient diffusion of reactant and intermediate hydrocarbon species. Weight gain studies find that the yield of nanotubes can be as high as 45 wt%.7 nm. The image illustrates remarkable abundance of individual and bundled SWNTs that are free of defects and amorphous carbon coating. The choice of methane is critical to the CVD approach to SWNTs. Bulk quantities of high quality SWNTs can be synthesized by optimizing the catalyst. our optimized catalyst consists of Fe/Mo bimetallic species supported on a sol-gel derived alumina-silica multicomponent material (Cassell. et al.. et al. 1998b. This is based on the results that high SWNT yielding catalysts exhibit large pore volumes in the mesopore regime (Cassell. We believe that the rate-limiting step in SWNT CVD growth involves gas diffusion. 1999b). Thus far. et al. et al.. 13. The diameters of the SWNTs are dispersed in the range of 0.7–5 nm with a peak at 1. Inset: an example of the frequently observed SWNT ends that are closed and free of metal particles. 115 . et al.. Within the methane CVD approach. 1999b).

1987. In contrast. et al. 13.. 1994. left panel) (Tibbetts. et al. catalysts with 116 . Careful high resolution TEM imaging of the SWNTs synthesized by our CVD method frequently observes closed tube ends that are free of attached or encapsulated metal particles (Fig. 1989. Tibbetts. 1999b). 13. Baker. The opposite ends are typically found embedded in the catalyst support particles when imaged along the lengths of the nanotubes. 1989. Kong.3 inset). 1983. 1998a. Cassell.1. 1990. Base-growth operates when strong metal-support interactions exist so that the metal species remain pinned on the support surface. Tibbetts.13. In the methane CVD method.. These observations suggest that SWNTs grow in the methane CVD process predominantly via the base-growth process (Fig. 1984. 1998b. Amelinckx.4 Growth Mechanism of SWNT The states of nanotube ends contain rich information about nanotube growth mechanisms. the tip-growth mode operates when the metal-support interaction is weak.. we find that enhancing metal-support interactions leads to significant improvement to the performance of the catalyst material in producing high yield SWNTs. This is rationalized by the increased catalytic sites and the facilitated base-mode growth processes.2.. On the other hand. et al. et al.

weak metal-support interactions lead to aggregation of metal species and reduced nanotube yield and purity (Cassell, et al., 1999b). Further understanding of the chemistry of catalysts and nanotube growth will undoubtedly lead to the synthesis of bulk quantities of high quality SWNTs approaching the kilogram scale.

13.2.5 Growth of Isolated Single-Walled Nanotubes on Controlled Surface Sites
The successful CVD synthesis of SWNTs in bulk forms has led to a straightforward synthetic route to addressable individual nanotube wires. By using substrates patterned with 1–5 µm wide catalytic islands, we obtain "nanotube chips" that contain isolated single-walled nanotubes grown from desired locations on the substrates (Kong, et al., 1998b, 1999; Soh, et al., 1999). Atomic force microscopy (AFM) images of SWNTs on a nanotube-chip are shown in Fig. 13.4, where the synthesized nanotubes extending from the catalyst islands are clearly observed. The diameters of the nanotubes are measured to be in the range of 0.7–4.0 nm, which is consistent with TEM results obtained with bulk SWNT materials. Some of the nanotubes have one end attached to a catalyst island and the other end terminated between islands. Nanotubes bridging islands with both ends attached to the opposing islands are also observed. As described in a later section, the bridging SWNTs allow reliable electrical connections to be made from the macroscopic scale to individual SWNTs. Thus, our controlled chemical synthesis opens up a new route to individual nanowire electrical circuits that are needed for fundamental and practical purposes.
Figure 13.4 (a) An AFM image of SWNTs grown from patterned catalyst islands on a silicon oxide substrate. (b) Image of an individual SWNT bridging adjacent islands.

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13.2.6 Growth of Suspended SWNTs with Directed Orientations
Obtaining single-walled carbon nanotube architectures with nanotubes in aligned orientations has been challenging. We have devised a synthetic strategy that leads to suspended SWNTs directed towards controlled orientations parallel to the plane of a silicon substrate. The SWNTs are suspended bridges grown from catalyst material placed on top of regularly patterned silicon tower structures. The synthesis approach begins with developing a series of liquid-phase catalyst precursor materials that allow for uniform film formation and large-scale catalyst patterning. A specific precursor material consists of ethanol (40 mL) and 2-butanol (20 mL) solutions of P-123 block copolymer (1.0 g) (Yang, et al., 1998a, 1998b), AlCl3 · 6H2O (2.4 g), FeCl3 · 6H2O (0.09 g) and MoO2Cl2 (0.004 g). Using contact printing (Xia and Whitesides, 1998; Ferguson, et al., 1991) of a flat PDMS stamp inked with a film of the precursor material, we selectively place the precursor on top of tower arrays pre-made on a silicon substrate (Cassell, et al., 1999a). Calcination at 700°C for 4 h leads to the formation of alumina/silica mixed oxides confined on the tower tops. Subsequent CVD growth using the substrate yields SWNTs emanating from the towers. Directed free-standing SWNT networks are formed by nanotubes growing to adjacent towers and suspended above the surface. When examining with an SEM, we observe that highly directional suspended SWNTs are formed on the synthesized sample. The directions of the suspended tubes are determined by the pattern of the towers. Well-aligned SWNT bridges are obtained in an area of the substrate containing isolated rows of towers as shown in Fig. 13.5(a), where suspended tubes forming a power-line-like structure can be seen. In an area containing towers in a square configuration, a square of suspended nanotube bridges is obtained (Fig. 13..5(b)). Directionality of the suspended tubes is simply a result of the rationally designed substrate. During the CVD growth, nanotubes emanate from the top of the towers. The nanotubes growing towards adjacent towers become suspended, whereas nanotubes directed towards other orientations fall onto the sidewalls of the towers (not easily resolved under SEM). In Fig. 13.5(c), we show a TEM image of a suspended SWNT bridge between silicon towers, and an image (Fig. 13.5(c), inset) showing the high resolution structure of the SWNT.
Figure 13.5 (a) SEM image of a suspended SWNT "power-line-like" structure. (b) SEM image of a square of suspended SWNT bridges. (c) TEM image of a SWNT bridge suspended between silicon towers. Inset: a high magnification TEM image showing the structure of a SWNT.

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The directed growth of suspended SWNTs presented here involves developing a new type of liquid phase catalyst material, contact printing of catalyst onto designed substrates and CVD synthesis. The method should open a new window in characterization and device applications of organized nanowire architectures in suspended states or after being transferred onto flat substrates.

13.3 Physics in Atomically Well-Defined Nanowires
It is well recognized that single-walled carbon nanotubes are ideal systems for studying solid-state physics in quasi one dimension (Dresselhaus, et al., 1996). SWNT wires have well-defined atomic structures and can be considered as molecule-like wires (Dekker, 1999). It has been actively pursued to elucidate their band structures (Dresselhaus, et al., 1996; Saito, et al., 1992; Mintmire, et al., 1992; Hamada, et al., 1992; Odom, et al., 1998; Wildoer, et al., 1997), quantum confinement (Tans, et al., 1997; Bockrath, et al., 1997; Cobden, et al., 1998), electron-electron (Tans, et al., 1998a; Bockrath, et al., 1999; Kane, et al., 1997; White and Todorov, 1998), and electron-lattice (Kane, et al., 1998; Kane and Mele, 1997) interaction effects in SWNTs. The remarkable sensitivity of a SWNT electronic structure on tube chirality and diameter requires addressing individual nanotubes in order to understand electron transport in various classes of nanotubes. Previous approaches to addressable SWNT electrical devices include randomly depositing SWNTs from liquid suspensions onto pre-defined electrodes (Tans, et al., 1997) or onto a flat substrate followed by locating nanotubes and patterning electrodes (Bockrath, et al., 1999). Results obtained with individual single-walled tubes and ropes include Coulomb charging (Tans, et al., 1998a; Bockrath, et al., 1999) and Luttinger liquid behavior (Bockrath, et al., 1999) in metallic tubes. Semiconducting SWNTs have been found to exhibit field-effect transistor characteristics at room temperature (Tans, et al., 1998b; Martel, et al., 1998; Soh, et al., 1999; Kong, et al., 1999). Nevertheless, the intrinsic electrical properties of various types of nanotubes remain to be fully understood.

13.3.1 Integrated Circuits of Individual Single-Walled Nanotubes
The synthesis of individual SWNTs at desired surface sites has enabled a controlled route to addressable SWNTs for systematic electrical measurements of nanotubes. With the SWNT chips described earlier, integrated nanotube circuits can be constructed by using a straightforward microfabrication procedure (Soh, et al., 1999; Kong, et al., 1999). Various types of metals are used to contact nanotubes including Ti, Ni, Nb, Cr, Au, Al and Ag. The contacting process places metal electrodes to fully cover the catalyst islands and extend over the edges by 0.5–1 µm. The individual SWNT bridges between islands leads to a significant number of metal-SWNT-metal electrical devices. Optical and AFM images of a representative device are shown in Fig. 13.6 In our samples, the lengths of individual SWNTs between electrodes were ≥3 µm. Degenerately doped silicon wafers with 500 nm thick thermally grown oxide on the surfaces are used as substrates. The heavily doped substrate is conducting at low temperatures and used as a backgate. Figure 13.6(c) shows the schematic structure of our devices.
Figure 13.6 (a) Optical image of SWNT integrated circuits. (b) AFM image of an individual SWNT device. (c) A schematic view of the device structure.

121

122

At low temperatures. Gate voltage =-10 V. (c) Current vs. a perfect (n. These individual SWNT samples remain to be in low resistance states when cooled to low temperatures. 13. The linear resistance of the sample decreases as the temperature is decreased.10 V gate voltage is found to lower the resistance of the sample (dashed line in Fig. and a slight upturn is observed below 30 K in the resistance vs. temperature R(T) for a metallic SWNT contacted by 20 nm/60 nm Ti/Au...7(a). If ohmic contacts are made between metal electrodes and the tube. 1998a.. 1996). These results suggest that the SWNT is of true metallic nature and correspond to a (n. 13..10 V at room temperature and 4 K exhibit linear characteristics near zero bias voltage. 123 . Bockrath.e. At 2 K. current vs. we have obtained a large number of low resistance individual SWNT samples in the range of tens to hundreds of kilo-ohms (length between the edges of contacting electrodes ≥3 µm).. However. Detailed transport data obtained with this sample are shown in Fig. 13. et al. it has been challenging to make good electrical contacts to SWNTs. the sample exhibits clear stair-case structures in the I-V (dotted line in Fig. (b) I-V curves recorded at 300 K. 13. Dashed line: R(T) measured under -10 V gate voltage. 13. et al. gate voltage curves measured under various bias voltages show fluctuations but the absence of periodic Coulomb oscillations. et al.7(c). 1998a. current vs.100 to 100 V find that the sample remains conducting in the entire experimentally accessible gate voltage range. and the resistance is 12 kΩ at 2 K. Solid line: R(T) measured under zero gate voltage. gate voltage curve recorded at 2 K under various bias voltages. n) armchair tube is conducting. n) indices are true metallic wires with finite density of states at the Fermi level (Dresselhaus. half of the resistance quantum h/e2. Using the approach of controlled SWNT synthesis and contacting. Figure 13.7.7(b). temperature curve (solid line in Fig. Coulomb blockade has been observed in individual metallic single-walled tubes or ropes due to high contact resistance on the order of mega-ohms (Tans.. the origin of these interesting features remains unclear at the present time. 4 K and 2 K respectively. a resistance of 6. i.7(a)). Coulomb charging effects have been the main physics studied in these samples (Tans. voltage I-V curves recorded under Vg = . et al. The lowest single-tube resistance is 12 kΩ measured at 2 K. 1999). can be expected (Chico. In Fig. 1996). measured under zero gate voltage). Bockrath. n) armchair type.. As shown in Fig. 1999).7 (a) Resistance vs.2 Electron Transport Properties of Metallic Nanotubes Single-walled armchair nanotubes with (n. Sweeping the gate voltage from .5 kΩ.3. 13. and transport along the length of the tube could be ballistic due to quenched phonon modes and the defectand impurity-free nature of the nanotube. At low temperatures.7(b)). Coulomb blockade behavior is not observed in this sample because highly transparent contacts have been made to the nanotube. However.13. Applying a . et al. et al.

124 .

13. n) SWNTs with m-n ≠ 3 × integer are semiconducting in nature and have primary energy gaps Eg ∞ 1/d. It is a common observation with our samples that upon varying gate voltage. et al. This gate dependence is far from negligible although much weaker than semiconducting SWNTs.5 kΩ resistance limit in metallic SWNT systems. et al. 1998). et al. Smaller diameter tube samples with d≤1. We present in this section temperature-dependent transport data of individual semiconducting SWNTs of various tube diameters.. only under certain gate voltages are pronounced proximity effects observable. Other types of metal typically lead to higher resistance. the resistance of metallic SWNTs can be changed by a factor of 2–4. nature of contact and transport mechanisms in semiconducting SWNTs have not been addressed. transport mechanisms through semiconducting SWNTs at various temperatures are elucidated.. et al. gate voltage data for the metallic SWNT (Fig.Among the various contacting metals investigated for SWNTs. Some of the variations could be due to metal-tube transparency changes under various gate voltages. We attribute this phenomenon to the fact that the transparency of metal-tube contacts (or junctions) is tunable by gate voltages. At 4 K. the samples are insulating and show gap-like region within ± 10 mV to ± 1000 mV in the I-V curves. to address the precise nature of the contacts and achieve the 6.7–3 nm. It is expected that the broken translational symmetry at a nanotube end allows strong electrical coupling between the nanotube and a metal (Tersoff. 1999). We find that semiconducting SWNT samples exhibit common characteristics but differ quantitatively.0 nm) tubes. et al. 125 ... The low contact resistance is also attributed to the controlled approach of nanotube growth and integration that allow metal electrodes coupling to the sides and the ends of a nanotube. where d is the nanotube diameter (Dresselhaus. The origin of non-periodic fluctuations in the current vs. we find that Ti tends to give rise to the lowest contact resistance. 1999). 1999).. Furthermore. which could be a significant factor in the observed low contact resistance of our samples. 1999).. The gap region is found to be larger for smaller diameter tubes.7(c)) at low temperatures remains to be fully understood. The semiconducting tubes appear to be hole-doped and their conductance can be diminished by applying positive gate voltages. The room temperature resistance is typically in the range of 200–500 kΩ for samples with relatively large diameter (d>2.25 eV according to band structure calculations (Dresselhaus. New possible mechanisms of hole-doping to nanotubes and the nature of metal-tube contacts are proposed. 13.5 nm exhibit higher resistance on the order of mega-ohms or higher. and temperature-dependent electrical properties remain unexplored so far (Tans. 1996). In this case. fundamental issues such as the origin of carrier type. Our growth method produces SWNTs with diameters dispersed in the range of about 0. et al. and the resulting semiconducting tubes have energy gaps about 1–0. Transport studies of this class of nanotubes have been limited to 300K. Martel. It remains a challenge.3. et al.. 1996). 1998b. however. The gate dependence of metal-tube coupling is also consistent with recent numerical calculations that found contact resistance to a SWNT depending on the Fermi energy of the tube (Rochefort. Temperature-dependent resistance of the samples shows that transport through the semiconducing tubes involves thermal activation with higher barriers for smaller diameter tubes. This is based on recent experiments that have observed superconducting proximity effect in SWNT samples contacted by superconducting Nb electrodes (Morpurgo. Also. suggesting enhanced metal-tube contact transparency by these gate voltages (Morpurgo.3 Electron Transport Properties of Semiconducting Nanotubes Chiral (m.

a gap 20 mV is observed in the I-V curve and the sample is insulating in the bias range V ≤ 10 mV (Fig. (b) show the room temperature I-V curves obtained with a d = 2. 1998b. 13. The sample exhibits a highly linear I-V with resistance 370 kΩ measured at zero gate voltage. 126 .5 V gate voltage.8(a). Inset: room temperature I-V characteristics.3 nm semiconducting SWNT (sample # S2) with Ni contacts recorded at 4 K.. temperature measured by using near zero bias voltages ( V ≤1 mV) under zero gate voltage is shown in the inset of Fig. 1998. Martel. (b) I-V curves recorded at 4 K for sample # S1 under various gate voltages. the resistance increases sharply and R(T) can be approximately fitted to exp(-Ea/KBT) with an activation barrier of Ea 4. (c) I-V curve for a d = 1. The insulating region is found to be significantly suppressed by applying a -1. Below 25 K. Positive gate voltages progressively reduce the linear conductance of the sample (Fig.8 nm length 3 µm semiconducting SWNT (sample # S1). 1999).8(b). applying a positive gate voltage leads to a larger insulating region in the I-V curve (Fig. temperature. Inset: linear resistance vs. The temperature dependence of resistance is weak from 300 K to 25 K..Figure 13. At Vg>3 V.8(b)). the conductance is suppressed by four orders of magnitude from that at Vg = 0. 1999. These I-V characteristics are signatures of hole-doped semiconducting SWNTs acting as p-type transistors as reported previously (Tans. At 4 K. 13. Kong.8 (a) Room temperature I-V characteristics of a d = 2..8(b)).8 nm semiconducting SWNT (sample # S1) contacted by 20 nm/60 nm Ni/Au. et al. et al. On the other hand.6 meV.8(a)). Soh. temperature. 1/T. et al. et al. 13.. The result of resistance vs. (d) Linear resistance vs. 13. Inset: plot of resistance in log scale vs. Figure 13. with an increase from 370 kΩ to 1 MΩ.

13.. 13. the I-V curve becomes nonlinear and the resistance is infinity below 40 K due to the appearance of a gap-like insulating region in I-V. It is also possible that interactions between a semiconducting nanotube and molecular species in the environment (including surface hydroxyl groups and other species on the SiO2) lead to the observed hole-doping effects.8(c) inset).EV. The room temperature linear resistance of the sample is 3. 13. We tentatively propose that a possible doping source could be charged species on the sample surface or trapped charges in the substrate near the SWNT. In our samples. The junction barrier height approximately equals to the separation between the nanotube Fermi level and the valence band EFV = EF . 1981). it is not plausible that the effect of work function mismatch (=Ni = 5.8(c). 127 . we have used titanium. Stray or trapped charges are known to exist in SiO2/Si systems and affect the electrical characteristics of conventional semiconductor devices (Sze.3 nm and length 5 µm semiconducting SWNT (sample #S2). 1998b). aluminum.7 V as shown in Fig. Hole-doping to nanotubes has been previously attributed to electron transfer from nanotubes to metal electrodes due to different work functions (Tans. The resulting semiconducting tube samples all appear to be hole-doped and show p-type transistor behavior. we show the results obtained with a d = 1.8(d)). Such doping mechanisms act over the entire length of a nanotube. and silver that have similar work functions as graphite. and magnesium and calcium with lower work functions than graphite for the contacting metals. et al. et al.9) and forms a Schottky-like junction with the p-type nanotube bridge. The linear resistance of the sample sharply increases as temperature decreases. metal/tube work function mismatch does not appear to be the origin of hole-doping in our samples. A band diagram model is presented in Fig. 1998).5 eV) can extend over the 3 µm long tube. (d). =NT 4. First. Thus. and can be well fitted into an exponential form R (T) exp (. we propose that each contact consists of a series resistance (black bar in Fig.Ea/KB T) with an activation barrier Ea 25 meV (Fig. At 4 K.9 for a metal-semiconducting tube-metal system to rationalize the obtained transport results.9 A proposed band diagram for a metal-semiconducting SWNT-metal system. Nevertheless. 13.5 eV vs.EV. a complete understanding of the precise doping mechanism requires further investigations. Figure 13.In Fig. 13. we consider that the nanotube is uniformly hole-doped along its entire length. Upon cooling. the insulating region is within ±0. instead of being localized near the contacts. Secondly.4 MΩ under zero gate and is dramatically increased by positive gate voltages (Fig. Furthermore. The junction barrier height Ea is determined by the separation between the nanotube Fermi level and the valence band EFV = EF . 13. Note that homogeneous hole-doping to SWNTs was also believed to be the case in a previous study (Martel..8(c).

(c). and can be fitted into I exp (. 1997).8(b). 13. (c)) find that current increases by three orders of magnitude after the turn-on. Thus far. Soh. et al. Under a high bias voltage.. 1994).4 Electron Transport Properties of Semiconducting Nanotubes with Small Band Gaps WNTs with (m. 1996) pointed out that the curvature of nanotubes leads to non-parallel pπ orbitals interacting with pπ-orbitals.c/V) where c is a constant. Thus. 1997). et al. 1999. 1997). n) indices m . et al. the band gaps scale as Eg 1/d2 about 2–50 meV for d = 3–0. Under significantly high bias voltages. 1997. the samples exhibits linear I-V curves (under zero gate voltage) since the junction barriers can be overcome by thermal energy Ea ≤ KB T = 26 meV. et al.. (1992) and White et al.8(b).7 nm (Kane and Mele. 1998. These theoretical work clearly pointed out that the curvature of SWNTs has non-trivial consequences to their electrical transport properties (Blase. whereas for SGS-SWNTs. the sample is turned into a conducting state. Louie and co-workers carried out first-principles ab initio calculations and found that the curvatures of small diameter SWNTs can lead to rehybridization of π* and σ* orbitals and thus altered electronic structures of SWNTs from those of flat graphene stripes (Blase.8 nm and 1. The band gaps for S-SWNTs scale as Eg 1/d about 0. The sample is in an insulating state near zero bias as shown in Fig. At 300 K.. semiconducting SWNTs. In scanning tunneling microscopy (STM) studies. Kane and Mele. However.. et al.7 nm. 1999). et al. 1998b. SWNTs exhibiting significant conductivity at low temperatures were believed to be metallic.8(a). and is determined to be Ea EFV about 4. Wildoer. true metallic armchair SWNTs. the semiconducting tubes are hole-doped to large degrees. Martel.. For this type of SWNT. 1994. These results suggest that electron transport through a semiconducting tube at low temperatures is via a tunneling mechanism. et al. metallic and semiconducting SWNTs were identified by probing the local density of states of nanotubes near the Fermi level (Odom. et al. Semiconducting tubes were identified when their conductance can be significantly modulated by gate voltages at room temperature and the nanotubes become insulating at low temperatures (Tans... 128 . 13. which causes the opening of a small band gap to result in a semiconductor from a semimetal. Kane and Mele categorized SWNT into three types.. thermally activated transport through the system is quenched. The mechanism of thermally activated transport at high temperatures and transport via tunneling at low temperatures is similar to that observed in conventional metal-semiconductor-metal systems by Lepselter and Sze (Lepselter and Sze. Kong. leading to higher barriers and thus less conducting states as seen in Fig. Analyses of the I-V curves (Fig. The expected energy gap for the d = 2. experimental work characterized SWNTs into metallic and semiconducting two general categories. In previous electrical transport experiments. 1997.6 eV respectively according to band structure calculations. 13.. no experimental evidence was reported so far to prove the existence of small-gap semiconducting SWNTs predicted by theory. Hamada et al. 1997).2–1 eV for d = 3–0. et al. electron tunneling occurs through the reverse biased Schottky-like junction. et al. At 4 K where KB T << Ea. 1997.6 meV and 25 meV respectively for samples #S1 and #S2. 1968) 13. (c). 1999... 1998.n = 3 × integer are semimetallic with zero band gap within tight-binding calculations based on pπ-orbitals alone.3 nm tubes are Eg 0. Large metal-SWNT contact resistance tended to cause Coulomb charging effects observed in transport measurements (Tans. and curvature induced small gap semiconducting SWNTs (Kane and Mele.The junction barrier is responsible for the observed thermally activated transport through semiconducting SWNTs. Bockrath.3.2 and 0. et al. Positive gate voltages cause the valence band shifting down away from the Fermi level. Nygard.

3 nm. beyond which further increase in Vg recovered the conductance of the SWNT sample. Controlled device fabrication for low metal-tube contact resistance is essential to the elucidation of the intrinsic electrical properties of SWNTs. This resulted in a valley in the conductance vs. (b) dI/dV vs. the conductance was observed to recover and increase with Vg.Vg) curve recorded under a constant source drain bias of V = 1 mV. Figure 13. determined by AFM topographic measurements. gate voltage curve. showing a resistance of 36 kα under zero gate voltage (Vg). 1999). 13. gate voltage (dI/dV . 129 .3 nm SWNT. which has long been realized as an obstacle to elucidating the nature and intrinsic electrical properties of SWNTs (Nygard. The I-V curves are highly linear. In this section.10(a). Figure 13. 13. Vg at room temperature. 13. et al.10(a). The current-voltage I-V curves obtained at room temperature are shown in Fig.10 (a) Room temperature I-V characteristics of an SGS-SWNT.. Inset: AFM image of the d 1.10(b).. We find that the electrical characteristics of small-gap semiconducting SWNTs are clearly distinguishable from that of true metallic SWNTs and semiconducting SWNTs with large primary band gaps. In Fig. we show the conductance vs. As Vg was further increased. Increasing Vg reduced the linear conductance of the sample and reached a minimum at Vg 5 V. Consistent with the results in Fig.Bockrath.10 shows a tapping mode atomic force microscopy (AFM) image of an individual SWNTs exhibiting small-gap semiconducting characteristics. 1997). et al. The diameter of the SWNT was 1. the conductance of the sample was suppressed by initial increase in Vg and was lowered by 4 times at Vg 5 V. we present the observation of individual semiconducting SWNTs with band gaps on the order of 10 meV.

Upon cooling the SWNT sample to 2 K. A grey-scale 2-D conductance map was obtained by plotting the conductance values at all of the (V. as shown in Fig. 13.5 V. In the central region of the map.5 to 10 V. under gate voltages in the range of Vg = 0 to 20 V with an incremental step of 50 mV. The conductance map exhibits symmetrical structures centered at V = 0 and Vg = V*g 8.11(a). within V -8 mV to 8 mV and Vg 7. we recorded 400 I-V curves in the source-drain bias range of V = -40 to 40 mV with an incremental step size of 400 µV. Vg) points. the sample is highly conducting in the corner regions of the map where V 130 . the sample conductance is highly suppressed and the corresponding resistance 5 MΩ. However.

We also measured the zero-bias conductance dI/dV under various gate voltages using the lock-in technique. 13.11(b). 13. as dips of reduced conductance are seen in dI/dV vs. bias voltage (dI/dV . we show conductance vs. A gap-like region with highly suppressed conductance is observed between Vg 9 to 12 V in the dI/dV-Vg curve. The corresponding resistance 20 kΩ. V. (b) dI/dV vs. 131 .g. and the high bias conductance is about 5 ×10-5 S. only slight dips are seen in the dI/dV curves near zero bias. (c) Zero-bias dI/dV vs. These results are consistent with the 2-D conductance data in Fig. the sample exhibits high conductance with fluctuations. The brightest color corresponds to the lowest conductance 1 × 10-7 S.11(c).> 10–20 mV and Vg 0 or 20 V. Outside the gap.11(a).11(a). 13. indicating a gap-like structure in I-V. However.e. These conductance curves shift downwards as Vg increases from 0 to 8 V. horizontal centerline crossing the suppressed region in Fig. then shift upwards upon further increase in Vg.11 (a) Grey-scale 2-D conductance plot log (dI/dV) at various (V. Vg recorded at V*g 8 V. Under Vg 8 V V*g (i.V) curves recorded under various gate voltages. 13. the conductance is highly suppressed for small biases V < 8 mV in the dI/dV-V curve.. V curves recorded at various Vg.. corresponding to 20 kΩ resistance for the SWNT. for gate voltages far away from V*g (e. 0 or 20 V). which is more than two orders of magnitude lower than that in the central region. as shown in Fig. Figure 13. In Fig. The darkest color corresponds to the highest conductance 4 × 10-5 S. The suppression is nearly exponential in V. Vg). The I-V curves are nonlinear near zero bias.

132 .

bias recorded under V*g (bottom curve in Fig.12(b)). gate voltage curves measured at 290 K. The band gap can also be estimated from the conductance vs.. when measured at gate voltages that are shifted from V*g(T) by a constant. as streaking lines are seen near the central region in Fig. we do observe significant conductance fluctuations upon gate voltage variations.5 eV/L (Bockrath. These fluctuations could be due to electron interaction effects. which leads to significant conductance as transport through the valence band can occur (p-type). 13. we determined the temperature-dependent resistance of the SWNT sample under conditions with fixed Fermi-level position relative to the bands at all temperatures. Thus.11(a) is 20 kΩ. 13. The low temperature data shown in Fig. At 2 K. the valley resistance was found to increase monotonically as temperature decreased. 133 . This gives an estimated band gap Eg α ΔVg' 7. transport through the SWNT under small bias voltages is thermally activated across a barrier Eg/2. The resistance decreased from 36 kΩ to 25 kΩ as temperature decreased from 290 K to 80 K. We also elucidated the temperature-dependent electrical properties of the small-gap semiconducting SWNT. gate voltage data shown in Fig.5 meV. We observed that V*g (valley position in a dI/dV-Vg curve. For Vg V*g. et al. The resistance measured at V = 1 mV increased with decrease in temperature below 80 K. 13. Measured at V*g(T). The resistance was found to scale as exp(-Ea/KBT) with Ea 6 meV (Fig. The linear conductance vs. Coulomb charging effects are not dominating the observed small-gap semiconducting characteristics. Vg = V*g(T)-5 V. the resistance of the SWNT was found to exhibit drastically different dependence on temperature. the resistance of the SWNT sample away from the suppressed region in Fig. where the gap region exhibiting highly suppressed conductance spans ΔVg' 3 V. 1997). 13.The results presented above clearly show the small-gap semiconducting nature of the SWNT. which is close to the resistance quantum h/2e2. the I-V curve became nonlinear with suppressed conductance near zero bias. The small-gap semiconducting nature of the SWNT is thus fully manifested.11(a). which is consistent with the fact that Coulomb charging is not the dominant phenomenon observed with the sample. Under Vg V*g. However. At 2 K. Under V*g where the Fermi level of the nanotube is in the middle of the band gap.11(c). 13.5 meV/V.12(a). temperature curve in Fig. To correct for this unwanted effect. 13. The low resistance points to excellent metal-tube coupling. we obtain α (ΔE+U)/ΔVg 2. resulting in an upturn pattern in the resistance vs. as the temperature was lowered. the suppressed region in conductance vs.11 exhibit no clear signatures of Coulomb blockade. energy level spacing ΔE 0. Upon further cooling. through which electron transport occurs (n-type). 60 K and 10 K under a bias of V = 1 mV are shown in Fig. gate voltage measurements. The typical oscillation period is ΔVg 200 meV.11(b)) suggests that the SWNT band gap is on the order of 8 meV. The drifts can be interpreted as due to changes in the electrostatic charge state of the substrate. This suggests that when the Fermi level resides inside the band gap. a barrier exists to transport and the conductance of the sample is suppressed at both room temperature and low temperature. corresponding to the gate voltage under which the Fermi level of the nanotube is in the middle of the band gap) drifted as temperature decreased. the Fermi level is inside the nanotube valence band. From the previously found Coulomb charging energy U 1. and L 3 µm. The gate efficiency factor α for our general sample geometry can be estimated by using Coulomb blockade theory on our high resistance (hundreds of kiloOhms) metallic SWNT samples that exhibit periodic Coulomb oscillations in conductance vs. 13. On the other hand. especially under low bias voltages ( V <10 mV). but their precise origins are not understood at the present time. the Fermi level is shifted into the conduction band.4 eV/L (nm).

twiston) scattering (Kane. Figure 13. 1/T measured under V*g(T). These results clearly show that. positive slope in dR(T)/dT can be attributed to reduced phonon (e. A possible reason for the upturn at low temperature could be due to small barriers existing near the contacts due to band bending of the heavily doped p. T measured under V*g(T)-5 V The SGS-SWNT sample described above was highly stable and allowed for reproducible transport data.12 (a) dI/dV vs. (b) Linear resistance vs. et al. In this quasi-metallic state. Note the shifts in V*g(T). (c) Linear resistance vs. when the Fermi level resides within the valence (or conduction band. the small-gap semiconducting SWNT behaves like a quasi-metal.12(c). Solid line: fitting of R(T) exp(-Ea/KBT) with Ea 6 meV.g. 1998) as temperature decreases.13. 60 and 10 K. upon repeated thermal cycles and loading/unloading the sample.or n-type SWNT. Nevertheless. respectively.. shift in V*g by several volts 134 .. data not shown). Vg curves recorded at 290.

11.1 Nanotube Molecular Transistors with High Gains Previous single-walled nanotube (SWNT) field-effect transistors (FET) obtained by randomly deposit SWNTs across electrodes exhibit low transconductance and voltage gain (Tans.8 nm tube sample (#S1) over a bias range of 3 to -3 V are presented in Fig. The I-V curves show marked asymmetry with respect to the polarity of the bias voltage when V > 1 V. 13. 1992. 1994.. 1998b. 1998). A shift in V*g had occurred between these measurements. Results shown in Fig. In the positive bias side.. Martel. 1997). In the negative bias side. This "dual-personality" depends on the Fermi level position relative to the energy bands of the nanotube. Excellent coupling from metal electrodes to various types of SWNTs are reproducibly obtained within our fabrication approach. Under a given gate voltage. At Vg = 3 V.10 and 13. (b) I-V curves recorded after exchanging the source-drain electrodes. This indicates slightly different environments felt by the nanotube during different cool-downs. Our controlled chemical synthesis and integration approach have led to single-walled nanotube transistors that "mimic" silicon based metal-oxide field-effect transistors (MOSFET) with similar I-V characteristics and normalized transconductance.3 nm. We have also elucidated the intrinsic electrical transport properties of SGS-SWNTs: either semiconducting or quasi-metallic behaviors. which leads to low contact resistance on the order of h/2e2 and facilitates the elucidation of intrinsic electrical properties of SWNTs. Figure 13. Our results provide direct transport evidence for the existence of SWNTs with small band gaps 10 meV.13(a). White. Blase.4 Integrated Nanotube Devices 13. et al. Out of 20 systematically characterized individual SWNT samples. The SWNT is not an S-SWNT with large primary band gap. the absolute current value is higher under a positive bias than under its negative bias. et al. 13.. the I-V curve essentially resembles that of a rectifying diode. with our semiconducting nanotube samples. Kane and Mele. The asymmetry in I-V becomes increasingly dramatic under higher gate voltages.was observed. the current increases monotonically as the bias voltage increases and does not show any saturation. The electrical properties of SGS-SWNTs can be clearly distinguished from other types of SWNTs described earlier.12 were recorded during a different thermal cycle from that shown in Figs. et al.4. We attribute the origin the observed small band gap to non-trivial curvature effects predicted to exist in small-diameter SWNTs (Hamada. we reproducibly observed an interesting feature in the I-V curves when high bias voltages were applied. et al. 13. First.13 (a) Room temperature I-V curves recorded with sample #S1 for V in the range of 3 to -3 V under various gate voltages. (c) Symmetrical I-V curves obtained by scanning V while biasing the two electrodes at -V/2 and V/2. since the observed band gap is 10 meV and is much smaller than 600 meV expected for an S-SWNT with d 1.. 13.. I-V curves obtained at room temperature with the d = 2. 135 . 1996. we observed three small-gap semiconducting SWNTs in electrical transport measurements. the current initially scales linearly as V but reaches saturation and stays constant at large negative biases. respectively. et al.

13(b)). Positive bias voltages still lead to higher absolute current values than negative biases (Fig. These results suggest that the observed asymmetrical I-V curves are not caused by asymmetrical parameters such as different contact resistances at the two metal-tube 136 .The asymmetry in I-V is found to be inherent to the metal/tube/metal system. I-V curves recorded after exchanging the source and drain electrodes show nearly unchanged asymmetry. 13. Furthermore.13(c)) by scanning V in the range of -3 to 3 V while biasing the two electrodes at -V/2 and +V/2. we find that symmetrical I-V curves can be obtained (Fig. 13. respectively.

35 obtained previously (Tans. Sample # S1 (Fig. a negative or positive bias voltage with absolute value on the order of 1 V locally depletes or increases the hole-carrier density in the nanotube segment near the drain. the transconductance is 0. Secondly. We conclude that for a significantly high bias voltage V. V ]. The [0. Normalized by the diameter of the nanotube ("channel width"). 1981). the nanotube can be considered to have a constant hole-density along its length. the approach of direct growth of nanowire materials into ordered structures represents a promising direction towards new nanoscale science and devices. high voltage gain and transconductance are obtainable with our samples.V ] configuration.interfaces. we derive a transconductance Ids/ Vg 200 nA/V. 1998b). Note that asymmetry is nearly absent in the I-V curves in the small bias regime ( V <0. Overall.. the Ids-Vds curves of our samples exhibit similar characteristics as silicon based devices (Sze. This phenomenon can be related to local carrier depletion and channel pinch-off by negative drain bias in a conventional p-type MOSFET (Sze. . On the other hand. et V=100mV al. From the linear region of the Ids-Vds curves. 1998). This method achieves atomically well-defined nanowires by bottom-up chemical routes.8(a)) exhibits positive voltage gain of ΔVds/ΔVg I=3µA 3 compared to the maximum gain of 0. Saturation occurs in the I-V curve for large V because of the competing roles of driving and gating of the drain bias voltage. The bias polarity associated asymmetrical I-V has been consistently observed in all of the p-type semiconducting SWNT samples that we have studied. We propose that the asymmetry in I-V is caused by local gating effects of the biased drain electrode. The negative drain bias effectively introduces an increase in the gate voltage localized near the tube section close to the drain. et al. which is two orders of magnitude higher than previous results with SWNTs (Martel. 1981). and wired-up architectures that normally require top-down fabrication or assembly techniques. Under a given gate voltage. such asymmetry is introduced into the system by the large applied bias voltage. The general 137 . under the positive bias configuration [0. 13.8(a). a higher barrier to transport is produced at the junction at the drain. Under a negative bias configuration [0. The high transconductance is a direct result of low resistance ( 370 kΩ) of the semiconducting SWNT system. Undoubtedly. Our results are significant in the realization of high performance nanotube based transistors. the electric field lines at the section of the nanotube close to the drain becomes suppressed or even reversed at large V .. First. resulting in a reduction of hole density in the section. 13.1 mS/µm and is comparable to that of a silicon p-MOSFET. 13. This leads to local hole enrichment (or equivalently barrier lowering) in the nanotube section near the drain. leading to a lower absolute current level when the system is negatively biased.1) as can be seen in Fig. and the I-V curve deviates to the higher current direction from the linear curve extrapolated from the small bias regime. the electric field lines can be substantially enhanced at the nanotube section near the drain electrode for V > 1 V. V ] bias configuration leads to higher current flow than the [0. Equivalently. The I-V curve thus falls below the line extrapolated from the low bias curve.5 Conclusions This chapter presented synthetic strategies that lead to various nanotube architectures useful for fundamental studies and potential applications of nanotube wires. . the current flow I is not solely determined by the absolute value of voltage V across the system and can be influenced by the bias configuration.V ].

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are important in high-performance engineering applications for high-temperature. 1985) is directed towards understanding their covalent and ionic nature through a study of scaling arguments based on the Phillips-Van Vechten scheme (Phillips. an additional empirical term is added to account for the depletion of bond charge with increasing ionicity. the goal of this effort is also to see if one can design a high-performance material by beginning with theories to select candidates for laboratory synthesis. As one of the computer designed structures. and high thermal conductivity. high-power.2 Theoretical Prediction A number of workers have published theoretical calculations for light-element compounds.. For the zinc blendes. 1973) for characterizing the covalent and ionic nature of tetrahedral solids by means of their spectral properties. 1997. Nanomaterials from Light-Element Composites 14. for example of carbon nitride polymorphs.1 Introduction For over 10 years a large amount of work worldwide has been directed towards obtaining an understanding of the new covalently bonded nanomaterials made from light atomic weight elements from the first row of the periodic table because of the novel microstructures and the extraordinary combination of physical properties (Wang. For purely covalent solids such as carbon and silicon. 1999). 1999.2. et al. In addition to the potential applications. 1973).1 Empirical Model An empirical approach was first developed by Cohen (Cohen. 14. 1985) to study the bulk modulus on the basis of the Phillips-Van Vechten scheme (Phillips.147 nm in length) and covalent ( 7% ionic) bonds (Cohen. 1989a. Such materials with high hardness and toughness. the bulk modulus scales as the average homopolar energy gap in the reflectivity spectrum divided by the volume of the bond charge. Veprek. For example. oxidation resistance. An early empirical model (Cohen. or high-frequency devices ranging from microelectronic to spaceflight industries.14. 1985. This leads to the bulk modulus varying as d-3. Investigators have also studied the phase transition under pressure and vibrational properties (Widany. this study provides a test of the effectiveness of first-principles calculations in materials science. high adherence. 14. The 142 . 1989b).5. chemical stability. The formula is modified further by adding a factor Nc/4. where Nc is the average coordination number. It is the purpose of the present chapter to survey the recent work which has been carried out and to detail the level of understanding which has been attained in the research of light-element nanomaterials. 1996). Other theoretical efforts have focused on ab initio band structural calculations and ab initio molecular dynamics (MD) simulations. Cohen proposed that carbon nitride should have diamond-like properties with a relatively isotropic arrangement of short ( 0.

1989). Eq.resulting relationship between the compressivity modulus B (Mbar)(1 bar = 1 × 105 Pa). 1989). structure. Therefore. in the range 0 to 0. including α-.1) we can easily find that the condition for large B is to minimize d and λ. A quasiparticle electronic band calculation of β-C3N4 was given by Corkill and Cohen (Corkill and Cohen. The B values obtained for a number of zinc-blende compounds from Eq. which indicates that short bond lengths and low ionicity are favorable for achieving large bulk moduli. the carbon nitride compounds should have high bulk moduli. pseudocubic-.43. this was ruled out by Liu and Cohen because in a hypothetical zinc blende C-N compound with nine valence electrons per unit cell the first antibonding band would be occupied (Liu and Cohen. 14.147 nm) and λ. accounts for the reduction in B arising from increased charge transfer. is 3. was given by Teter and Hemley within the local density approximation (LDA) (Teter and Hemley. 1 and 2 for Groups IV. From the GW correction.5 (Liu and Cohen. Because of the small atomic radii of carbon (0. As a semi-empirical method depends only an input parameter d.1 nm) of the interatomic bond can be written as The ionicity parameter. cubic-. the lowest 143 . and graphitic-C3N4. The most obvious candidate structure to be used as a prototype for a first-principles investigation of the properties of a covalent solid formed between carbon and nitrogen is the simple zinc blende structure. The band gap of β-C3N4 was 3. Liu and Cohen suggested a hypothetical carbon-nitrogen compound wherein carbon is substituted for silicon (Liu and Cohen. ionicity λ and length d (0. 1996). λ.(14. This would distribute charge in the antibonding band and hence it is doubtful that such a structure would be stable with respect to other cases. III-V and II-VI semiconductors.1) are in excellent agreement with experiment and rival the costly first-principles calculations for accuracy.2.070 nm) and λ<1. and physical properties of carbon nitride polymorphs. it is possible to use the theory to design materials with predictable properties.1) yields B is 410–440 GPa which brackets the calculated value for diamond. λ = 0. III-V and II-VI semiconductors. By using estimates of d ( 0. 1985).56 eV given by Yao and Ching using first-principles local-density calculations (Yao and Ching. 1994). As this structure is a Group IV-V material. this expression gives results which are as accurate as first-principles total-energy calculations (Cohen. 1993). β-.2 First-Principles Study Further first-principles studies of carbon nitride compounds are motivated by an early discussion.(14. Systematic first-principles calculations of the relative stability.077 nm) and nitrogen (0. 1994). respectively. This is in agreement with experimental results showing an increase of ionicity and a loss of covalency in going from Group IV. However. From Eq. Liu and Cohen chose to use an ionic parameter. 1990). Nc. By evaluating the known β-Si3N4 structure.(14. The average coordination number. A β-C3N4 structure was first suggested by Cohen based upon knowledge of the known β-Si3N4 (Cohen. 1988). An ab initio variable-cell-shape molecular-dynamics algorithm was used to investigate the stability of three carbon nitrides with composition C3N4 (Liu and Wentzcovitch.

ion beam deposition. Hamada. Using dc magnetron sputtering.. 1995). et al. such as boron carbonitride (BCN) and silicon carbonitride (SiCN).. et al.. 1998). 1994). obtained carbon nitride films with N/C value up to 1. 1994. 1992).. et al. this group also calculated the vibrational property of C-N structures (Widany.. 1985). These results imply potential applications of BCN nanotubes or nanofibers in nanosized electronic and photonic devices. et al.. Chubaci. have also attracted considerable attention. amorphous carbon nitride thin films were grown by Han and Feldman using a feedstock of CH4 and N2 (Han and Feldman. A pulsed high-energy plasma technique was used by Peng et al. et al. Watanabe. Lu. 144 . using sputtering techniques (Yu. Fujimoto and Ogata (Fujimoto and Ogata. et al. and high-pressure pyrolysis.4 eV while the direct gap at the minimum gap in diamond. 1995). Niu. These gaps are even larger than Badding and Nesting presented a thermodynamic analysis of the formation of a more carbon-rich C4N3 under pressure (Badding and Nesting. chemical vapor deposition.. 1997. Some small crystalline particles embedded in amorphous C-N films were observed by Yu et al. the ternary compounds.indirect gap is predicted to be 6.. and Fujimoto (Ogata. sputtering. (Peng. It is also expected that the band gap of BCN nanotubes decreases for the series of intermediate phases from insulating hexagonal boron nitride (h-BN) to semimetallic graphite (Miyamoto. Okada et al. Sjöström. Li et al. 1996). 1993).. 1996). 1998). is 6. such as plasma. According to theoretical calculations. 1997). et al. 1994) reported on the formation of nitrogen rich C-N materials by 0.20 by relatively high-pressure rf magnetron sputtering (Okada. laser ablation. 1993).. and Ogata.75 eV. and Lieber deposited covalent solid carbon nitrogen films on Si (100) using low-energy (about 1 eV) atomic beam-assisted laser ablation (Niu. A study on the amorphous state of carbon nitrides for a wide range of stoichiometries and densities was performed by using a molecular-dynamics simulation (Weich.0 keV N ion beam. et al. In a capacitively coupled rf plasma reactor. Most recently. et al.5–10.. a tremendous amount of experimental effort has been applied to synthesize light-element nanomaterials by a large variety of the more readily available techniques. 14. et al. besides excellent mechanical properties (Hernandez.. et al. Electron diffraction indicates that β-C3N4 is a viable structure for these crystallites.. 1996). et al. synthesized CNx thin films with a fullerene-like microstructure (Sjöström. 1995. et al. (1995) to deposit CNx films.3 Synthesis by Chemical Vapor Deposition (CVD) Ever since the theoretical prediction by Cohen in 1985 (Cohen. possible evidence for the stabilization of β carbon nitride was reported by several groups using CVD. 1994). et al. Their results show that C3N4 and C4N3 form in a similar pressure range. et al. Recently this group claimed that they had obtained thin-film C-N materials with <50 at % nitrogen (Zhang. 1995). it is relatively easier to control the electronic properties of BCN nanotubes since these properties are mainly determined by the atomic composition and atomic configuration (Blasé. et al.33 (Li. reported polycrystalline C3N4 films deposited on Si(111) with N/C ratio of 1.. Most recently. By the same method. 1996) and Bursill et al...

the gas mixture is introduced into it with desired concentration.1 Bias-Assisted Hot Filament CVD A bias-assisted hot filament CVD (bias-HFCVD) was designed and used to synthesize light-element composites (Chen. et al. The general deposition procedure is carried out as below: after the chamber pressure of 1×10-3 Torr (1 Torr = 1. 1995). 1992). et al.. Nanocrystalline diamond.3 mm) is heated to dissociate the mixture. Among the techniques used so far. 1998a. A dc bias (both negative and positive) with a power supply (500 V × 1 A) can be used to generate discharge plasma between the filament and the substrate. which is introduced from the chamber top. et al. The depositions are performed from several minutes to more than 10 hours for different purposes. BCN and SiCN with various microstructures have been also reported experimentally. Yu. et al. 1999. chemical vapor deposition (CVD) is the most successful for growing light-element composites. 1999. 1999). 1999). et al. Chowdlhury. and a carbonized tungsten filament (= = 0. and a Ta wafer of dimensions 10 mm × 20 mm × 0. et al. et al. et al. et al. BN. The negative bias plays an important role. turbostratic BCN structure (Yu and Wang.. 1998) have been synthesized. 14.1 Schematic of the bias-assisted HFCVD. Wang.3. Since the first study on BCN by Badzian et al. BCN nanotubes (Way. (1972). et al.333×102 Pa) is pumped. Then the filament is heated and the negative substrate bias is applied... sputtering. 1999) and carbon nitride nanofibers in high yield were deposited on silica substrate by pyrolyzing melamine over laser-patterned thin films of Fe and Ni catalyst (Terrones. Fahmy.2 mm is used as the substrate holder. which is useful to increase the activation of nitrogenous precursors. 1999. 1996a. et al.. and other techniques (Chen. 1997a.. 1996b. 1997). 145 ... 1999). et al.high-energy ball milling. Figure 14. 1999).. et al.1). the cubic BCN phase (Weng-Sieh.. a tantalum (Ta) mesh 30 mm × 40 mm in area is installed above the filament at a distance of 15–20 mm. and BCN microrods (Yu. Jagielski. A systematic investigation on SiCN has been performed by varying the growth parameters over a wide range (Gong.. Distinct from a conventional apparatus. as we have found that carbon-rich films with no perfect crystal grains have been obtained in the experiments without the application of the bias. 14. High pure gases are mixed as the reactive source. The vacuum chamber is a water-cooled stainless steel tube with a size 45 cm in diameter and 60 cm in length (see Fig.. Well-aligned carbon nitride nanotubes were synthesized in anodic alumina (Sung..

50–400 V.3. et al. The system. consists of an independent vacuum processing chamber equipped with a electron cyclotron resonance (ECR) plasma source.The main experimental parameters are set: filament temperature. Yu. 14. 146 .. negative bias voltage (Vmesh . 5–8 mm..333 × 102 Pa) prior to deposition using a turbomolecular pump. A 2. In the experiments.Vsub<0).45 GHz. 1996a. nanocrystalline carbon nitride (Chen. 14. Two magnetic coils. A radio-frequency (rf) heater with power controlled dynamically by a temperature controller keeps the substrate temperature quite stable during processing. 1998). The vacuum chamber is usual evacuated to about 10-7 Torr (1 Torr = 1. By using this system. 50–350 mA. 1997a).2.. which are cooled by a water-circle system. DC glow discharge current. The ion species generated by the combination of magnetic field and microwave excitation are accelerated from the plasma to the substrate by a negative dc bias. 1500 W microwave power supply produces microwaves that are guided through a quart window to the ECR plasma processing chamber. 1999) and well-aligned boron carbonitride nanofibers. driven in a mirror configuration establish an 875 G magnetic field. et al. which voltage is in the range of 0–90 V. 1800°C–2100°C (measured by an optical pyrometer). et al. substrate temperature 750°C–950°C (measured by a W25Re thermocouple fixed on the back of the substrate). 1999. turbostratic boron carbonitride (Yu and Wang. we have successfully obtained polycrystalline diamond (Chen. The flow ratios of the reactive gases are controlled by mass-flowmeters respectively.2 Electron Cyclotron Resonance Microwave Plasma-Assisted CVD (MPCVD) Electron cyclotron resonance microwave plasma-assisted CVD is already commercialized. filament-substrate distance. shown in Fig.

. because of the low or negative electron affinity (NEA) of diamond (Himpsel. In undoped CVD diamond films. Cold cathode field emission has been demonstrated in CVD polycrystalline diamond films. Particularly. As a result.4 Uniform Size-Controlled Nanocrystalline Diamond Films Diamond and related materials have been extensively studied for their novel mechanical. Figure 14. 1999). chemical and electrical properties. and carbon nitride/diamond/silicon multilayers. special interest is focused on its field electron emission (FEE). polymerized carbon nitride nanobells (Ma. et al. 1999).. which are highly disordered or contain 147 . the bulk conductivity is dominated by the space charge limited current (SCLC) (May. grain boundaries. By using this system. of which even a prototype flat panel display was made (Kumar and Schmidt. et al. 14.. which is believed to have potential applications from flat panel display to power transmitters. et al. 1995). It has been reported that defect-related energy states or sub-bands may play important role in supplying electrons and forming conduction channel for field emission (Wisitsora-at. Since intrinsic diamond is a wide band gap (5.. 1997). 1998).the substrate temperature can be varied from room temperature to over 1500°C.45 eV) insulator. the NEA is almost useless unless there exists an effective mechanism supplying electrons to the conduction band.2 Schematic of the ECR-MPCVD. we have successfully obtained nitrogen-incorporated nanocrystalline diamond (Wu. et al. 1979). et al..

The first series of films are grown by using different CH4 flow rates from 2. Figure 14.3 TEM images of the nanocrystalline diamond films grown with N2/CH4.999%) and methane (99. Thus a direct way to improve the FEE properties of diamond is to reduce the film grain size. uniform size-controlled nanodiamond films were obtained by Wu. The inserted selected-area electron microscopy (SAED) image shows a typical ring pattern of the nanocrystalline diamond.1 sccm.5 sccm for (a) and 2. which is composed of the diamond crystallites at the size of 8 nm.1 Deposition with CN4/N2 Precursor Film deposition is carried out using an ASTeX 2115 microwave plasma-assisted CVD system with a maximum microwave output power is 1500 W (Wu.co-deposited graphite impurities. Figure 14. reaching up to 40% as roughly estimated from the image. where the CH4 flow rates are 3. et al. and the content of amorphous carbon is much lower.0 µm diamond paste and then ultrasonically cleaned in acetone. et al. All as-deposited films in the experiments present very smooth surface.3(a) reveals the nanocrystalline nature of the film.5 and 2.. The content of amorphous carbon in this film is relatively high. 2000). 1999).3(a) and (b) shows the transmission electron microscopy (TEM) images of the two films. 148 . they have attracted more and more attention. and give an emission threshold of about 3 V/µm. et al. can be well controlled by the deposition parameters. Figure 14. et al. Because of this and other unique features of nanocrystalline diamond films. where (a) and (b) are grown with 3. using hydrogen addition to N2/CH4 precursor in microwave plasma-assisted CVD (Wu. Inserted is the SAED pattern.1 sccm for (b).. (2000) fabricated nanocrystalline diamond films by plasma enhanced CVD (PECVD) using C60/Ar/H2. The film microstructure.4. ethanol and deionized water consequently. Very recently. have been suggested as the main conduction channel through CVD diamond films. observed an emission threshold as low as 1 V/µm on nanocrystalline diamond films prepared from industrial diamond nanopowders.3(b) shows a larger grain size at about 20–30 nm. respectively.. Polycrystalline molybdenum and (100)-oriented Si wafers are used as the substrates. respectively. The film in Fig. 14.1 to 8.. such as low friction and transparency. while the N2 is kept at 150 sccm and no H2 gas is used. below 5% as estimated from the TEM image. The as-grown films have a deep black color under visible light. including the diamond grain size and the content of the graphite impurity. High pure nitrogen (99. 14.9%) gases are employed as precursors. Zhu. or O2/Ar addition to the H2/CH4 precursors.4 sccm. which are first polished by 1. Zhou et al. embedded in amorphous carbon textures.

where the full-width-half-maximums (FWHM) of these peaks are significantly broadened due to the confinement effect. B 149 .XRD spectra show strong diamond (111) and (220) feature peaks. λ the wavelength of X-ray. The broadening of the diamond peaks provides a way to determine the average diamond grain size in the films. where D is the average diamond grain size. According to the Scherrer equation D = λ/(Bcosθ).

On the other hand. with the decreasing of CH4 concentration in the precursors. the change of the amorphous carbon content cannot be shown in the XRD spectra. It is found that within a certain range of CH4 concentration (certain sccm CH4). Raman spectra of the nanocrystalline diamond films grown with different CH4 concentrations are shown in Fig. which is caused by the size effect of the nanoscale diamond grain (Walter and Messier. It should be noted that even in the film with lowest graphite content. although the quantitative values of the diamond grain sizes obtained by these two methods are not exactly the same due to the residual stress and defects in the films. There is an additional peak at about 1150 cm-1. Here we take the strongest diamond (111) peak for analysis.5. and Gaussian fitting is used. the diamond grain size does not show much deviation. since X-ray diffraction (XRD) is insensitive to non-crystalline phase.. the diamond grain size becomes larger. It provides additional evidence for the nanocrystalline nature of the films.the integral width of the peak. the 1150 cm-1 peak becomes weak with the decreasing of CH4 concentration. The spectra consist of two wide peaks around 1560 cm-1 and 1350 cm-1. showing that the graphite content is reduced in these films. probably because the graphite contents in the films are relatively high. Talin.4. Secondly. This confirms the existence of graphite phase in our films as observed by TEM. Figure 14. for example of the film grown with 2. But as the CH4 flow rate is reduced to 3 sccm or below. respectively. the diamond 1332 cm-1 peak appears clear.4 Influence of CH4 concentration on the diamond grain size of the films grown with N2/CH4.1 sccm CH4 flow rate. and θ the Bragg angle. 14. First. This is inconsistent with the TEM results. 1990. indicating that the diamond grain size gets larger. Figure 14. This is because that the graphite phase has much higher resonance cross section than diamond. 14. In addition. and the graphite cannot be completely removed without addition of hydrogen to the precursors. which correspond to the G band and D band of graphite. These are all consistent with the TEM and XRD results. A weak diamond peak at 1332 cm-1 is presented. For a series of films grown with different CH4 concentration. the calculated diamond grain sizes are shown in Fig. 150 .5 Raman spectra of the nanocrystalline diamond films grown with different CH4 concentrations. et al. the diamond signal at 1332 cm-1 is still some what weak. 1996). two findings can be derived by the Raman spectra.

By comparing the two images with that in Fig. where the diamond films can be grown with very low CH4 concentration.4. only etching effect is observed. the diamond grain size increases from 8 to 20 nm (5 sccm H2). In fact.To study the influence of CH4 concentration on the film growth rate. Figures 14. where the CH4 is fixed at 3. 151 . 14. It means that pure nanocrystalline diamond films with controllable grain size can be obtained by varying the H2 concentration during growth. there is completely no film growth. colors change significantly from deep black to gray and then to transparent under visible light. such as 0. the film thickness is measured by a profilemeter.5 sccm.5%.0 and 10. It is found that the growth rate decreases nearly linearly with the CH4 concentration. This is in contrast with the deposition of polycrystalline diamond films with H2/CH4 precursors. a new deposition parameter. to the precursors. 14. When the CH4 flow rate is reduced to about 1. we then introduce a small amount of hydrogen (0–10 sccm). with the increasing of H2 flow rate. respectively.2 Influence of Additional H2 on Microstructure In order to further control the microstructure of the nanocrystalline diamond films.6(a) and (b) show the TEM images of the films grown with H2 flow rate at 5. it can be observed that with the increasing of H2 gas concentration the films.3(a).0 sccm. nearly pure nanocrystalline diamond films are shown in the images. where the same growth condition is used except for the addition of H2 gas. the graphite phase is greatly reduced. Secondly. and the film growth rate is calculated by dividing the film thickness by the growth time. First.5 sccm. apparent morphology evolution can be found. and then to 50 nm (10 sccm H2).

0 and (b) 10.3%. 152 . respectively. where the CH4 flux ratio is fixed at 2.0 sccm.Figure 14.6 TEM images of the nanocrystalline diamond films grown with H2 flow rate at (a) 5.

the surface stabilizing mechanism is simultaneously introduced. In fact.XRD and Raman spectra also confirm these results. to the CH4/N2 precursors. whereas by using traditional H2/hydrocarbon precursors polycrystalline diamond films are usually obtained. making it easy to grow large-size diamond particles.. the diamond grain size and graphite content can be easily controlled. the peak at 1150 cm-1. we can conclude that: (1) The microstructure of the nanocrystalline diamond films can be varied by either the CH4 concentration or the H2 concentration. Furthermore. the atomic H plays two key roles in the deposition of CVD diamond films. This value is well consistent with that estimated by TEM images. the diamond growth would takes place rather from a new diamond seed. 14. The dopant concentrations are around 1021 cm-3 for all the films measured. and nanocrystalline diamond films can be easily obtained. Based on the above analysis. Controversely. At the same time. Secondly. It is known that H can selectively etch off non-diamond phase to get pure diamond. we propose a surface stable growth model here.. The results show that the two series of the films with or without hydrogen are highly doped with nitrogen irrespective of the CH4 concentration or the H2 flow rate. It means that the diamond grain size has exceeded the value needed to generate this peak. When the H2 gas flow rate increases from 0 to 10 sccm. 153 . disappears in the films grown with higher H2 of 7. and thus determines the diamond grain size. There is a very clear evolution of the peak. an independent parameter. (2) By introducing H2 gas. and the graphite impurity can be almost completely removed from the films. Hence.3 Nitrogen Incorporation Secondary ion mass spectroscopy (SIMS) has been carried out on a CAMECA ims 4f. First. we find that the film growth rate of this series of films decreases with increasing of H2 flow rate. Thus with the help of atomic H. et al. The evolution of Raman spectra with the increasing of H2 flow rate is obvious. The amount of the additional hydrogen gas determines how stable the growing surface is. and at the same time the terminated H on the diamond surface also plays a role to stabilize the diamond growing surface (Walter. the relative strength of the 1332 cm-1 diamond peak to the graphite bands (G band at 1560 cm-1 and D band at 1350 cm-1) increases significantly with the increasing of H2 flow rate. the formation of new diamond can easily take place on the existing diamond surface. If we introduce H2 to the gas mixture. 14.0 sccm. The results show that the diamond grain size can be adjusted in a wide range (0–50 nm). we believe that the atomic N does not have the stabilize the diamond growing surface. no film growth but only etching effect is found.4 Surface Stable Growth Model In order to explain why the nanocrystalline diamond films can be easily obtained in the N2/CH4 environment. When the H2 flow rate increases to 15 sccm.4. where the FWHM decreases very quickly with the increasing of H2 flow rate. 1990).5 and 10. the selective etching of non-diamond phase of the atomic H results in the deposition of the pure nanocrystalline diamond films. where 10 keV positive Cs ion is used.4. which is indicative of the nanosize diamond crystallites. This means the graphite content is greatly reduced. in the N2/CH4 environment. the average diamond grain size increases from 8 to 50 nm.

The results of the films grown with CH4 higher than 4. et al. but soon turn bad with further increasing of H2. atomic N is found to have a similar effect. the emission threshold becomes rather high. there is no observable emission even when the applied field strength reaches 30 V/µm. in the film grown with 10 sccm hydrogen flow.5 sccm H2. graphite works as a conduction channel from the back-contact metal to the film surface. In the current test the anode-cathode distance is kept constant at 100 µm.5 to 2. The film acts as the cathode adheres to a metal base. It is found that with the decreasing of the CH4 concentration the FEE property of the films is significantly improved.. It seems that N has a relatively stronger etching effect to diamond phase as compared to the atomic H in a CH4/H2 environment. as the films grown with lower CH4 concentration have less non-diamond impurity. in which a two-layer structure consisting of amorphous carbon and diamond is proposed. In order to explain the FEE mechanism of the nanocrystalline diamond films. Furthermore.5 to 10 mA/cm2. For the large-size diamond grains. It is worthy to note that the FEE result obtained from the film grown with 2.5 sccm. which must be 154 . In such a structure. 1998). A molybdenum probe with tip area of 1 mm × 1 mm is controlled by a stepper and acts as the anode. The I-V characteristics of the films are measured by varying the applied voltage. 1999).1 sccm CH4 is among the best up to date (Okano. the diamond grain size is a critical factor determining the tunneling probability. the present results are measured on a surface without any treatment. and the maximum emission current decreases significantly. As electron from the diamond/graphite interface must tunnel through diamond to vacuum. et al.. We find that there are two main factors dominating the field emission property in this process: (1) the diamond grain size and (2) the graphite content in the film. Thus electrons will first tunnel through the diamond edges and then emerge from the diamond surface. A plausible explanation is given to this type of field-induced electron emission phenomenon.Atomic H has a selective etching effect of diamond and non-diamond phases. The corresponding F-N plots well fitted by straight lines indicate that the field emission process can be explained by a tunneling mechanism. In the film grown with 5. From our experiments. Zhu.5 sccm. and the emission current is read from a Cathylet 617 nm. electrons can only be emitted from the regions close to the edge. the emission properties of the films show some improvement at the beginning when the H2 flow rate increases from 0 to 2.5 Field Electron Emission and Transport Tunneling Mechanism The FEE test is carried out in a high-vacuum system with a base pressure below 5 × 10-7 Pa.4.7 shows a schematic of this process. while the maximum emission current increases from 0. the emission threshold drops from 15 V/µm to 1 V/µm. As H2 varies from 0 to 10 sccm and CH4 is kept at 3. 1996. When the CH4 flow rate decreases from 3.1 sccm. But this effect is certainly weaker than atomic H. because there is no observable electron emission even when the applied field strength reaches 30 V/µm (which is the upper limit of our high voltage supply). A repeatable abrupt change of "on" and "off" states of emission is observed at two corresponding specific fields during circling of both increasing and decreasing applied gap fields (Chen. while on the surface the diamond has a relatively low or even negative electron affinity. et al. a model based on the graphite/nanodiamond mix-phase structure is proposed. as when the CH4 concentration is reduced to about 1.. In particular. which enables the growth of pure diamond films with low CH4 concentration when we use CH4/H2 as precursors.9 are not shown here. there will be no film growth but only an etching effect. Figure 14.0%.0 and 7. 14.

the diamond/graphite interface area will decrease. we believe that the positive effect of reducing graphite content can overcome the negative effect of increasing grain size. For the small-size diamond grains. Figure 14.7 Schematic diagram of the field electron emission from diamond/graphite mixed-phase structure. our experimental results can be understood by the following discussion. the decreasing of CH4 concentration will (a) increase the diamond grain size from about 8 nm to 20–30 nm. But when the graphite content is further reduced to a critical value that is not enough to fill the gaps. with the increasing of H2 flow rate from 0 to 10 sccm. This process will greatly increase the emission site density. but the 155 . The increasing of the diamond grain size has a negative effect on the FEE. and the field emission properties will turn bad. As to the other series of the films grown with addition H2. As to the first series of the films grown without H2. So the trend is similar to the previous case. on the other hand. The decreasing of the graphite content. the diamond grain size increases from 8 to 50 nm. has a positive effect on FEE. When the graphite content is large enough to fill the gaps between the diamond grains. Although the change is not very significant. this effect is relatively small. Based on the above model. The graphite content is another critical factor because the emission takes place from the diamond/graphite interface. and (b) reduce the graphite content from 40% to a much lower value as shown by the TEM images.thin enough for an electron to tunnel through. and the emission property will rapidly be degraded. the electrons can effectively be emitted from a larger area or even the whole diamond particles. so an improved FEE property is achieved. Further decreasing of the graphite phase will even make it not enough to form a conducting channel through the film. Combining the two effects. the decreasing of the graphite content will increase the diamond/graphite interface area and thus enhance the electron emission.

Chowdlhury. et al. 1997a. small grains ( 0. for instance. et al. the field emission property of the films rapidly turns bad. 1995a.. sp2 coordination. threefold. when the graphite content has not been reduced too much. et al. Two years ago. 1996a. et al. et al.1 α and β Structures Figure 14. later showed that compact. By optimizing the deposition parameters. which is linked together by other nitrogen atoms in a nearly planar.1 µm) and nanocrystallites were grown in the films and identified to be β-C3N4 by Yen and Chou (Yen and Chou. et al.8 shows an ideal β-C3N4 structure. 1997a. 14.. 1997. Thus the FEE property of the films may be improved as a combined effect of the changes of grain size and graphite content. deposited crystalline C-N films with Si content less than 5 at % on Si (100) substrates by using a microwave plasma-assisted CVD (Bhusari. 1999)... 1997b). graphite plays an important role in the field emission of the nanocrystalline diamond films. the graphite content decreases very fast with increasing H2.8 Unit cell of a β-C3N4 structure. our group reported the results of the stabilization of nanocrystalline carbon nitride films (Wang. 1999. Veprek et al. a novel FEE property can be obtained.much large grain size have a more negative effect on FEE.. The unit cell with space group P31C has 28 atoms. Very recently. 156 .. The α-C3N4 structure is described as an ABAB… stacking sequence of layers of β-C3N4 (A) and its mirror image (B). et al. Figure 14. Chen... Bhusari et al. some American groups showed new evidence of β phase CN structure (Fahmy. 1997). i. 1999). the decreasing of graphite content has a positive effect on FEE. uniform films of the composition of C3N4 could be prepared by plasma CVD in an intense nitrogen discharge. The simple hexagonal phenacite structure with P3 symmetry is formed by 14 atoms: eight nitrogen and six carbon. Guo. but they did not obtain crystalline films (Veprek. By CVD. In addition. The carbon atoms are fourfold sp3-coordinated by nitrogen atoms in a regular tetrahedron. and the films grown with higher H2 have little graphite phase as revealed by TEM and Raman.5. as seen in the experiment. et al. 14. indicating that the graphite content in the films has been reduced too low to result in a strong negative effect on FEE.. 1999. But after this point. At the beginning. 1995). 1997.5 Nanocrystalline Carbon Nitride Films The investigation and development of carbon nitride has been a subject of intense research for the past years (Wang. Jagielski. 1995b). In this case.e.

1989. 1996a. c = 0. 1997c). β-C3N4.624 nm.5 eV per cell or an average value of 5.The earliest accurate calculation of the structural and electronic properties of β-C3N4 was performed by Liu and Cohen.. 1997b..20–1.236 nm) with relative N/C ratios of 1. 1990). as shown in Fig.5%. et al. c = 0. Teter and Hemley. By pseudopotential total energy approach they calculated the cohesive energy of β-C3N4 to be 81. This moderately large cohesive energy suggests that β-C3N4 is at least a metastable structure.60 on nickel are in good agreement with the ab initio calculations (Liu and Cohen. 1997a).3% and 2. 1993). Figure 14. where they gave the indirect band gap of 3.9. Well-faceted nanocrystallites consisting entirely of carbon-nitride network on nickel substrates are obtained from tens of nanometers to several micrometers. The experimental lattice constants (Chen.9 SEM of several C3N4 columns on a nickel substrate. 157 .638 nm. 1997a) of α-C3N4 (a = 0. 1990. 14. The successful synthesis of mixed-phase C-N films has prompted us to consider whether we can get a specific C3N4 phase film and the necessary experimental parameters. The first attempts to control the methane concentration and to add a fraction of hydrogen were reported by us to see the influence on the growth mechanism (Chen.4648 nm) and β-C3N4 (a = 0. Nearly pure crystalline C-N films.. Corrected GW study shows that both α and β carbon nitrides are wide band gap materials (Corkill and Cohen. which are composed of α-C3N4. et al.8 eV per atom.2 eV (Liu and Cohen. respectively. 1996) by less than 1. et al. and other unknown C-N phases were prepared on silicon and nickel substrates (Chen.

obtained a group of CN films with a relatively higher concentration of the unknown CN phases (Guo. which are not related to the formation of other compounds of the participating materials. et al. but to the formation of C3N4.275 nm. A detailed study of the TEM micrographs and SAED patterns of the monoclinic grains with different main crystal axes has been presented. The comparison with theoretically calculated vibrational densities of states and calculations utilizing Hooke's law enables the correlation of the measured phonon features with C3N4 phonon modes (Werninghuas. 14.. Guo et al. 1998). Some columns with prismatic tetrahedrons in morphology are observed..5.556 nm and c = 0. et al.8–1. In order to identify their structures. 14. more effort is being given to TEM and XRD.For these samples micro-Raman spectroscopy measurements are performed.3 Monoclinic Structure A monolinic CN structure with some relatively larger grains was identified in the CVD growth films (Guo. The N/C ratio of the new tetrahedral phase is about 0. 1997a). From the scanning electron microscopy (SEM) and TEM 158 . On the basis of XRD and TEM results. et al. the lattice parameters for the new tetragonal CN phase are determined as a = 0.2 Tetragonal Structure By applying selected-growth parameter in bias-HFCVD.0 by energy-dispersive X-ray (EDX).. 1997b). Further corresponding SAED patterns are taken for the tetragonal phase with different shapes and crystal axes (orientations).5. The spectra show several sharp lines in the spectral range from 500 cm-1 to 1600 cm-1. It is noticed that not only these tetrahedrons but also some grains with irregular shape present tetragonal symmetry.

. Combined with TEM.10 shows the center of a CN grain. et al. β and tetragonal CN phases in morphology.5. therefore. et al.5. 159 . 1998). 0.115 nm. it is found that most of the monoclinic CN grains exhibit irregular surface morphology. Guo et al.results. further XRD tests identify the new monoclinic CN structure with lattice parameters of a = 0.5 Carbon Nitride/Diamond/Silicon Layers It is known that both diamond and CN are wide band gap materials with high hardness. A better approach. tetragonal and monoclinic CN phases. and then the carbon nitride films are grown (Wu. β.209 and 0. The experiments are carried out electron cyclotron resonance microwave plasma-assisted chemical vapor deposition (ECR-MPCVD) apparatus. Sjöström et al. A two-step growth mode has been adopted in which a diamond layer is first deposited onto the substrate (Si or Mo). The planes observed with ring and fingerprint shapes indicate that pentagons are presented in the structure. With this identification. et al. c = 0..0. b = 0. The main difference is the basal planes. Figure 14.5065 nm.. The EDX analysis shows that the N/C ratio of this new phase is 0. pointed out that this structure is different from both graphite and turbostratic carbon.2801 nm and β = 96°. et al. which is also proved by our further test that the Si 2p signal is not present in the XPS spectrum. Nitrogen concentration is below 30 at % by RBS analysis. and high thermal conductivity. will be to integrate the superior properties of CN films with the mature technology of diamond. since the technology of growing diamond films is now well established and it is very easy to deposit high-quality polycrystalline diamond films on various substrates. high wear resistance.3.4 Fullerene-like Structure From quantum-chemical calculations and photoelectron spectroscopy. 1997b). discussed in section 14. crosslinked by sp2-hybridized bonds (Sjöström. In the present structure they are interlocked with covalent bonds of a much shorter bond length than that of the van der Waals bonds between the basal planes in graphite. Sjöström et al.10 SEM of the center of a CN cluster on diamond layers. 1998). claimed that the nearly pure crystalline CN films on nickel substrate by bias-HFCVD are mainly composed of α. However. Figure 14.. et al. The CN films are usually composed of many hillocklike crystal grains without prismatic morphology as deposited directly on silicon and nickel substrates (Chen. 1995).2.347. while is similar to that of fullerene-like buckey-onions. The structure can be described as graphite-like with interplanar distances of 0. which looks like a sunflower composed of many small CN fibers. 14. it should be noted that the atomic arrangement and the accurate stoichiometry are still unknown at the present time for these two new phases (Guo. proposed a fullerene-like microstructure to consist of a network of buckled sp3-hybridized CNx planes. 1997a).120 nm as obtained from SAED patterns.5–1. 14. HRTEM is performed for the samples prepared by mechanical cleaving. 1996a. The SEM is used to study the surface morphology of the film before and after CN deposition (Wu. which is quite distinguishable from those of the α.. It can be seen from the images that the diamond layer is quite dense. The CN films are deposited on Si (001) substrates by dc magnetron sputtering of a graphite target in pure nitrogen discharge.

it is found that there is no clear difference in the C 1s peaks. 1993).. Fujimoto and Ogata tested the amorphous CN1. The defect type is analytically thought to be dislocation clusters agglomerated by an interstitial-type defect. The peak shape and bond energy remain almost unchanged after deposition. there is absolutely no N signal in the film before deposition.94 films deposited onto tungsten carbide substrates by a Knoop type diamond indenter with a 10. In addition. only the full-width-half-maximum (FWHM) value are slightly enlarged from 1. 1999a). et al.0 gf (1 gf = 9. Further study shows that the nitrogen concentrations in the films are almost kept as a constant when the substrate temperatures vary from 100°C to 700°C. showing that the diamond film does not contain nitrogen impurities.5. a clear N 1s peak appears at 398. For the N 1s results. This value is different from the binding energy of molecular nitrogen at 404 eV.4–1.4 eV. hardness is only one of many properties which such a material has to meet (Veprek. which suggests a stable CN phase has formed.3 eV to 1. The reported Knoop 160 .From typical X-ray photoemission spectroscopy (XPS) C 1s spectra of the films before and after CN deposition. 14. 1999). Most defects in the CN/diamond/silicon multilayers are introduced by an extended growth of the original defects in Si substrate determined through layer-by-layer tomography.81 × 10-3 N) load (Fujimoto and Ogata. The importance of this property can be illustrated by the fact that today more than 40% of all cutting tools are coated by wear-resistant coatings and the market is growing fast.2–398.5 eV.6 Physical and Chemical Properties In most machining applications. defects in this structure are investigated by infrared light scattering tomography (Ma. But after deposition. proving that the N atoms are chemically bonded to C atoms.

. 1995). et al.. et al. et al... He. Large area field emission has been observed from thin C-N films (Chen. et al.. Lowther.3 W/(m · k) at 300 K. 1994.. These results present the superhard nature of the C-N bonds. 1997). First-principles calculations are performed for the structural properties of hexagonal β-Si3N4. 1994).709 nm and c = 161 . 14. In addition. but even so there is no direct hardness test for β-C3N4 because no high-quality single crystals are available at present time. et al. they found that the thermal conductivity of the C-N film is 0. nanoindentation of the film shows an elastic recovery of 85%. et al. et al.8 to 1. 1996). β-C3N4.. 1997). using UV transmission spectrometry for a nitrogen-rich C-N film (Ogata.. et al. 1999). which is opposite to nitrogen implanted diamond-like films.. et al. et al. Recently. studied the electrical properties of carbon nitride materials synthesized on quartz substrates by pulsed laser deposition (Zhang. et al. 1996c) thermal chemical vapor deposition (Bendeddouche. 1990). 1999). All the results show that carbon nitride is a very good electrical insulator and thermal conductor for high-performance electronics. et al. much work remains to be accomplished.1). RF nitrogen plasma-assisted pulsed laser ablation (Thärigen. and constants α and c are reduced (see Table 14. As more C atoms are substituted for Si in β-Si3N4. 1996). 1997).. ion implantation (Uslu.. Zhang et al.hardness of these samples is 6500 kgf/mm2(1 kgf/cm2 = 9.. et al. et al. which is closest to that for diamond ( 100 GPa) (Sjöström. and two model structures of β-Si2CN4 and β-SiC2N4 (Wang. It is found that the increase of resistivity with increasing nitrogen composition is highly nonlinear. 1998. 1992. The superhardness of 60 GPa is obtained from a CNx film with fullerene-like microstructure. Although the recent spate of success on CN research is impressive. The synthesis of high-quality and large CN crystal with interesting predicted properties remains a challenge for the future. Chen. In addition.. The averages of the calculated lattice constants for the four systems. ion or plasma sputtering (Novikov..43 Mbar).. 1997) and theorectically (Wang. Bulk modulus and lattice constants α and c have been obtained by fitting the total energy calculations to the Birch equation of state. Wu et al. This should be compared to the Knoop hardness of 5500 kgf/mm2 for c-BN made by the same experimental setup.81 eV for a crystalline C-N film with small amount of silicon (Lin. 1998b). Apart from its extraordinary mechanical property.. Another study presented an optical band gap of 3. Recently. et al.81 × 104 Pa). reported high resistance of C-N films against acid and electrochemical etching (Wu. comparable to that of diamond (4. et al. α = 0. et al. and plasma-assisted (Zhang. An optical band gap of 2.44 Mbar(1 bar = 105 Pa). This value is among the highest observed for any type of amorphous materials. 1998).. Fabrication of SiCN films was realized by reactive magnetron sputtering (Komateu. carbon nitrides show great promise in transport properties.6 Nanocrystalline Silicon Carbonitride Films The SiCN compounds have also motivated much attention because they exhibit some new features other than those of mixtures of crystalline Si3N4and SiC phases. the bulk modulus is observed to progressively increase up to 4. the first ternary crystalline SiC2N4 and Si2CN4 have been studied both experimentally (Riedel. 1996).7 eV was determined by Ogata et al.

371 0.. the silicon content increases linearly and nitrogen decreases. especially carbon and nitrogen.1 Deposition with Nitrogen and Methane 14. though the energy transferring efficiency between Ar and N atoms is much lower than that between Ar and Si. Gong et al. It suggests that the flat part. The chemical composition of the films is studied by Auger electron spectroscopy (AES) depth profile and EDX. on a sample grown at a median ratio.372 0. appear to be close to the experiments.1 Calculated lattice constants and bulk modulus of Si3N4.372 0. in the films is discussed on the basis of XPS analyses.2 7. these results have been confirmed by Lowther (Lowther. 14.52 2. while a small amount of oxygen is also found.8 5. 162 . 1999).272 nm. around the C-N nanocrystals.0 3. respectively (Chen.57 2. a thin-film layer (about 0.30 6. At lower CH4/N2 flow ratio. The sputtering rate used here is about 5 nm per minute. et al. 14. Moreover. the silicon atoms only come from the substrates. Si2CN4.19 4.3 µm in thickness) fully covers on the substrate surface.0 3. α = 0. The deposition of SiCN film is saturated. et al. of the films is mainly composed of Si and N elements.5% is used..0.43 By using bias-assisted hot filament CVD method. so not enough silicon atoms further diffuse from the substrates.263 nm. By EDX the atomic ratio of carbon and nitrogen is about 3:4.1.39 c/α 0.6. Wang.1 Influence of Methane Flow Ratio In the present experiments. 1998). As the depth increases. while the crystals lose surface symmetry when a high ratio of 3. 1999). For depth profiling with Ar+ ions. the facets of the crystals continue to integrate.72 2.84 2.11. This generally results in N concentration lower than the true value.372 B0(Mbar) 2. the density of the clusters is relatively higher. Recently. and there is abundant silicon element as shown in Fig. the overall carbon content of the remaining flat film is much lower by AES depth profiling after 2 min sputtering. 1996a. The effect of deposition parameters on the morphologies of the films is demonstrated by SEM images. SiC2N4 and C3N4 α(Å) Si3N4 Si2CN4 SiC2N4 C3N4 c(Å) 2.6.. The relationship between deposition parameters and the chemical environments of the elements. After 30 min deposition. The films with some embedded nanosize crystals are observed by SEM.92 6.44 B′0 3. Table 14.87 3. et al.65 7. have synthesized SiCN films under a wide variety of deposition conditions (Gong. yet N atoms are preferentially lost due to weak binding at the surface and high diffusivity in the sputter damaged solid. Besides the embedded clusters.706 nm and c = 0. The uniqueness lies in the mere reactive Si source totally from Si substrate and combination of thermal decomposition and plasma enhancement. which demonstrates that some typical clusters are composed of hexagonal columnar crystals. The preferential loss of N atoms has been observed in amorphous CN films when they are annealed or exposed to an electron beam.

7 eV (Karcher. It is readily assigned to Si-N bond existing mainly in the nitride overlayer of the Si substrate (Wagner. higher gas pressure (3 kPa). Kubler et al. the main N 1s peak is ascribed to N-Si bond. et al. et al. They found that the nitridation is rapidly saturated at high temperature and limited in thickness.5 eV at 800 eV.11 AEG depth profile of a SiCN sample with 100 sccm N2 and 3. the latter reasonably corresponds to C-Si and/or C-C bond. 1994). respectively. a thick nitride overlayer is formed. It is supposed that C-N bonds exist in the nanosize crystals. and plasma enhancement and etching applied here. There are apparently two XPS peaks around 286. Considering the higher temperature (>800°C). The line broadening could be explained as the presence of 163 .while carbon content remains constant.5 eV for silicon. 1982).5 sccm CH4 at the substrate temperature of 850–900°C. Compared with the C 1s binding energy of graphite at 284. Due to the low carbon concentration.. while the nanosize C-N crystals shown are simultaneously grown under suitable local conditions in this layer.6 eV and 284.0 eV and of silicon carbide at 283.. 1984). nitrogen diffusion and penetration into the substrate could be promoted. the binding energy of which is around 398. the thickness of nitride layer is estimated to approach 100 nm. From the slope of nitrogen profile. The XPS Si 2p spectra of the samples show only one bonding state near 101. 1988).8 eV. Figure 14.8 eV.. The XPS C 1s and N 1s spectra of the samples show both carbon and nitrogen have more than one bonding state. The film compositions and chemical bond stages are analyzed ex situ by XPS with a VG ESCALAB MKII system where Mg Kα line is used and the energy resolution is about 0. the former with higher binding energy can be assigned to C-N bond because of the larger ionicity of nitrogen atoms (Ogata. Thus. et al.. studied thermal nitridation of Si (100) surface by NH3 from room temperature to 800°C (Kubler. et al. Therefore.

and above 1100°C.1%. Therefore. only some samples prepared at very high temperature exhibited a few diffraction peaks attached to Si3 N4. 14. the particles become less than 100 nm and form big cauliflowers. the deposition rate (about 12 nm/min) is found to increase slightly. 1984). this can be attributed to C-N bond in the sample that contains some C-N particles. The XPS C 1s and N 1s spectra of the samples show the impact of the introduced hydrogen gas on the chemical states in the films. et al. there are many polyfaceted crystalline particles with a size of 500 nm. Methane and Hydrogen: Influence of Hydrogen Flow Ratio When hydrogen gas is introduced into deposition..complex local environments for N atoms. As shown by SEM.2 eV in the XPS spectrum of the sample grown at a temperature above 1100°C. but their positions shift slightly apart when the temperature increases from 850°C to over 1100°C. When the hydrogen ratio is increased. The proportion of C-Si/C-C eases quickly as temperature rises.8 eV.. the SiCN films prepared at high temperature could be characterized as SiN/SiC mixture. 1999).6. SEM shows the changes in morphologies of the films at increased hydrogen flow ratios.1 sccm is probably more advantageous to C-N bonding. et al. As the temperature increases. XRD analysis indicates that there is some crystalline Si3 N4 content in those films. However.6. If the assignment is true. The Si 2p peaks change little except for a small one at 99.1. 14. higher temperature results in second nucleation on previous crystals and disorder of crystal orientation (Gong. Furthermore. If a perfect crystal morphology reflects an ideal bonding structure. When the hydrogen concentration is small. regular crystals disappear and gross tiny particles are left. A smaller percentage of C bonds are ascribed to C-N and more to C-Si/C-C in the samples of CH4 with 1.5 eV of C 1s. This binding energy is a bit lower than the 286. some samples are prepared in three different temperature ranges of 850–900°C. 1994). which are relative to disorder or small crystal size. It indicates that C-N bonds could be unstable at high temperature.0 sccm and 3.5 sccm. the growth speed (about 100 nm/min) is elevated by about 10 times. As hydrogen ratio is increased. et al. Finally. the inference above would be consistent with the changes in the crystal forms. more carbon bonding 164 . Consequently. the XRD peaks are low and broad. It suggests that a median CH4 concentration of 2. When the temperature is raised to above 1100 °C.. 900–1000°C. On account of the strong peak at 286. AES depth profile exhibits about 10% carbon content in the film. there is still a little C-N bonding content and most bonds belong to C-Si/C-C. the N atoms should be bonded to sp3-hybridized C rather than sp2-hybridized C (Zheng. the particles become smaller and agglomerate in balls in size of 1 µm. Considering the abundance of C-Si/C-C in this sample. respectively.2 Influence of Substrate Temperature In order to study the temperature influence. But the crystalline contents in the film are still very limited. it may be linked with Si-C bonding. the structures and properties of the films differ from those of pure Si3 N4. In XRD analysis.2 Deposition with Nitrogen. 1996). There also exist two C 1s states in the XPS spectra. but the possibility of assignment to Si-Si is not precluded (Kaplan. When the hydrogen content is small. It is noted that N 1s exhibits another peak at 396. with a fixed CH4/N2 ratio of 2.6 eV for CN2 reported previously (Marton.

. The broadened peak suggests local disorder of silicon bonds in this sample with 30 sccm hydrogen at 950–1000°C. The depth-profile illustrating its chemical composition remains constant in a bulk of at least 50 nm thick. Simultaneously. while nitrogen appears almost purely N-Si bonds once hydrogen is applied. Compared with the situation without hydrogen. 14. such as NH. One possible reason to have a distant Si diffusion during the deposition is due to the hydrogen addition and ion bombardment which activate some Si or Si-H ion clusters above the substrate surface with the assistance of the negative bias and high substrate temperature. NH2. The total film thickness is estimated to be 1 µm or so by SEM cross sectional images. It seems that a few N atoms in the SiN network are replaced by C atoms and that C and N atoms are bridged by other atoms. whose binding energy increases to 285. For the uniformity of the films. that means a microscopic mixture of SiN and SiC compounds occurs in the particles due to the function of hydrogen.. 14. for there exist similar reactive species.3 Lattice-Matched Growth Model It should be noticed that some beautiful Si containing CN flowers are observed in Fig. Starting from random nuclei only those crystals with matched lattice to the substrate by an angle γ will survive. ion bombardment of negatively biased Si substrate under cathode plasma sheath is essentially applied. It obeys a "lattice-matched selection". used electron beam evaporation of Si surface under an NH3 ambient. whereas all the others are gradually buried. Then. more and more crystals nucleate on the faces of the formed crystals. H. the two peaks are observed to shift apart slightly as the hydrogen ratio increases. 1998). is the lattice match.transfers from C-N to C-Si/C-C and finally all become the latter. Thus the nitride overlayer becomes thicker and more uniform. 165 . To deposit SiNx thin films. the same as before. 1988). the solid-gas interface diffusion and reaction in the two comparable systems would apply some common mechanism.0 eV in Si 2p spectra.6. Kubler et al. It is reasonable to link the Si-CH4-N2-H2 and Si-NH3 systems (Kubler et al. Therefore. only those new crystals with a matched lattice to the faces by an angle will continually grow.12 after 40 min deposition by HFCVD. It is composed of many columnar crystals with hexagonal facets of 20–200 nm in across radiating outwards. etc.5 eV when the hydrogen concentration reaches to 30%. et al.12 A silicon-containing CN cluster on Si substrate. A possible growth mechanism is proposed. Figure 14. Here. Previous works in CNx alloys have shown an important dependence of the electron energy core level values on x (Ronning. which is ascribed potentially to Si-Si bond. which determines the probability of survival. the hydrogen expedites the interface reaction by rapidly producing larger amount of activated Si atoms near the substrate surface. As growth proceeds. The crucial property. There are also bonding states near 99.

Theoretical calculation and experimental study indicate that the BCN compounds possess semiconducting property between those of semimetallic graphite and insulating h-BN (Liu.1 Morphology and Composition 166 . The concentrations of H2 and CH4 in the gas mixture are kept at 37% and 4%. respectively. The filament temperature is about 2050°C.. The total gas flow rate is 100 sccm and keeps a constant during the deposition. The film compositions are changed by varying the B2 H6 concentration from 0. 14. 1999). The importance lies in that the electric property of the BCN compounds can be controlled by varying atomic composition and atomic arrangement (Yu. 1996).7 Turbostratic Boron Carbonitride Films Due to the structural similarity between graphite and h-BN. CH4. the solid solutions of BCN with graphite-like structure were proposed and prepared (Yu and Wang. et al.. H2.14. and the substrate temperature is about 800°C.7.0%. and B2 H6 (diluted in N2 at the concentration of 10%) are used as reactive source gases.. et al. High purity N2. Watanabe.3. The BCN compounds are prepared in a bias-assisted hot-filament chemical vapor deposition apparatus discussed in Section 14. 1999).1. et al.5% to 3. 1989.

39 C0.. Three different regions for BCN film growth are divided.54) at 1273 K. or N are observed.2 Turbostratic Structure 167 .51 C0.13. are calculated from areas under Gaussians using atomic sensitivity factors. B0. At temperature below 1073 K. From XPS spectra of the films grown at temperature above 1073 K some heteropolar bonds between substrate Mo and elements B. and (e) 1273 K.54 N0. and below 973 K (Yu. (b) 973 K.09) is much lower than that of C (0. B0.26. et al. The N concentration (0. It is indicated that at all temperatures the binding energies of B 1s.26. Figure 14.3.83 C0. around 1073 K. The chemical compositions. and 397. The C concentration is its lowest at 1073 K.5 eV.51 C0.31 N0.37 C0.18. (c) 1073 K. 284.34 N0. and it reaches the highest at 973 K. (d) 1173 K. The formulas of the BCN compounds deposited at different temperatures are as follows: (a) 873 K. the interference of Mo element is dramatically decreased. C 1s. however. B0.From SEM study it is manifested that the morphology of the deposited BCN films on Mo substrate depends greatly on the substrate temperature. B0. the BCN compositions are determined mainly by substrate temperature. They are above 1173 K.37) and B (0.7.23 N0.09. see Fig. 14.36 + B0.35 N0.17 + B0. 14.64 C0. and N 1s peaks are centered at 189.13 with substrate temperatures.30 C0. Generally speaking. and it seems a boron carbide phase formed at this temperature. C. which are shown in Fig.36. As the C and N active species are sufficient for the formation of BCN compounds in the process. 1999). It shows that there exists a stable phase in the films. B0.7. the N concentration decreases with increasing substrate temperature. 14.13 Chemical composition of B-C-N phase in deposited films versus substrate temperature. respectively.

which is larger than pure graphite (0.333 nm) (May. Figure 14.. %.72 C0. The crystallinity and d-spacing of the BCN films are independent of the film compositions. It is shown that the films are composed of small size grains. 168 .14 XRD results of BCN films with different chemical compositions (a) B0.. et al.32 C0.Figure 14.3336 nm). It is believed that the three kinds of B. et al. The wide (002) and (100) diffraction peaks reflect the nature of the turbostratic structure. where the hexagonal BCN network sheets are irregularly stacked in the directions of the c axis.38.15. The same case is also obtained even when the B concentration reaches 70 at. (c) B0.13 N0.3348 nm).12 C0.45 C0. The interlayer spacing of the obtained BCN compounds is determined to be 0. 1979). and N can be incorporated into the turbostratic structure with unlimited concentrations from graphite to graphite-like BCN to h-BN.30 N0.71N0.47. (e) B0.33.17.17 N0. boron carbide (0. It is noted that different from most of the early reports the peak positions here do not change with the film compositions. and boron nitride (0. Well-crystallized graphite-like structures are only observed at small amount of B or N doped into carbon layers or C doped into h-BN films.54 C0.36 C0. Takahashi. Apart from the turbostratic BCN no other phases are found in the spectra. C. and the crystallinity does not change much with composition. 1992. (f) B0.14 shows the X-ray diffraction (XRD) patterns of the BCN films on Si substrate for different chemical compositions.21 N0.349 nm. (b) B0.34.13 N0. (d) B0.

The HRTEM images of the BCN compounds are shown in Fig. 14.15. It clearly shows the turbostratic nature of the BCN films. The crystallinity is inhomogeneous in the films. Mostly, the deposits are the mixture of the turbostratic and amorphous domains, and in some cases the layers are embedded in the amorphous domains. The codeposition of the layered structure and amorphous domains indicates that the kinetic factor as structural fluidity and concentration distribution of active species play a key role in the formation of the BCN structure during the CVD growth. The layer continuity is frequently obstructed by the amorphous domains and defects, and the size of the turbostratic region ranges from several to over 50 nm. The layers are randomly oriented with various angles, and the curved layers with various curvature are formed. It is believed that the crossed layers are bonded with each other at some junctions. Even by adjusting experimental conditions over a wide range, only turbostratic structure is obtained in the present study. Because of the different atomic radius of B (0.076 nm), C (0.067 nm), and N (0.060 nm) the randomly incorporated B and N atoms in the graphitic structure cause local distortions and thus induce sheet curvature. The formation of the turbostratic structure may also be related to the poor structural fluidity at the low growth temperature and the over-high decomposition rate of B2H6 during the CVD process. It is known that the crystallinity of the turbostratic BCN films will be improved by heat treatment at high temperature of 2000°C (Filipozzi, et al., 1995) and the crystallinity of h-BN also improved with increasing growth temperature (Takahashi, et al., 1979).
Figure 14.15 HRTEM image of the turbostratic BCN structure.

14.7.3 Raman and Photoluminescence

169

Two very broad asymmetric bands centered at 1544 cm-1 and 2935 cm-1, respectively, are presented in the Raman spectrum. The band centered at 2935 cm-1 is characterized by second order Raman scattering. Different from other reports, no distinguishable D and G band, which are in general presented in Raman spectra of poor graphitized or amorphous carbon and carbon related materials, are found in the spectra (Yu, et al., 2000). It is found that the band width and band position remain almost unchanged with changing film composition. This implies that the film structures are about the same in this composition range. The change of the band intensity with film composition is probably related to the increase of antisymmetric vibrations with increasing B content. The Raman results here are consistent with that of XRD and HRTEM. In order to further determine the bonding states of the deposited BCN films, IR measurements are made. All the IR spectra show broad absorption band from about 1150–1670 cm-1. The absorption of this broad band increases with increasing B content in the films. This broad absorption band is believed to correspond to the broad Raman band centered at 1544 cm-1. Due to the incorporation of the B and N atoms into the graphite network and the breaking of network symmetry, the Raman active band becomes IR active. This broad absorption band is formed by the overlapping of a diversity of vibration modes. It is well known that the vibration characteristic absorption frequencies of some cluster or bond in a polyatomic molecule are affected by its atomic environments, so the differences in film composition and structure will cause the shifts of absorption frequency. The room temperature PL results of the BCN films are obtained for various compositions (Yu, et al., 2000). The broad PL bands show the characteristic of amorphous materials. It is found that with increasing the B content the PL peak energy shifts from about 2.80 to 3.40 eV. This shows that with increasing boron content the band gap of the BCN compounds increases, which is consistent with the prediction that the electronic structure of the BCN compounds can be controlled by changing its composition. It is indicated that the BCN materials emit blue to violet to ultraviolet light for different film compositions. It was reported that the PL peak energy at room temperature BC2N is 2.07 eV (Watanabe, et al., 1996). Because of the exceptionally high energy of emitting light, BCN compounds are interesting and important candidates for blue-light emitter.

14.7.4 Field Electron Emission
Furthermore, we have studied the field emission behavior of the BCN films (Yu, et al., 1999). The films used for field emission tests are deposited on polycrystalline molybednum substrates with film compositions of B 19 at. %, C 60 at. %, and N 21 at. %. The F-N plot almost follows a linear relationship, which indicates a Fowler-Nordheim tunneling mechanism. When assuming that the BCN film is an ideal plane emitter with a field enhancement factor β of 1, then the work function = = 0.044 eV is obtained from the slope of the straight line. Such values have been reported by different authors for α-C (Silva, et al., 1997), diamond-like carbon (Lee, et al., 1996), and h-BN (Sugino, et al., 1997). The emission current of 0.31 nA can be detected at the applied electric field of 4 V/µm, which is regarded as the threshold electric field. The maximum emission current of 0.31 mA is obtained at the electrical field of 13 V/µm. Although even lower threshold fields are reported for nanodiamond and carbon nanotubes, the BCN films have attractive advantage as field emitters for their smooth surface, low cost, easier fabrication, and better mechanical properties. Furthermore, it is expected that the field emitting properties of the BCN films can be improved by adjusting composition and structure from amorphous to turbostratic to crystalline.
170

14.8 Polymerized Nitrogen-Incorporated Carbon Nanobells
Carbon nanotubes were first studied by Iijima. For a practical application, however, a uniform doped nanotube is still a remaining challenge. Polymerized nitrogen-incorporated carbon nanobells are prepared from the source gases of CH4 and N2 by MPCVD discussed in Section 3.2 (Ma, et al., 1999b). Mesoporous silica plates (Novak, 1993) containing catalytic iron and nickel nanoparticles are used as substrates, these nanoparticles being essential for both the initial nucleation and the subsequent growth of carbon nanotubes. The working temperature (500°C) of the substrate is well below the operating temperature (900–1000°C) employed in the MPCVD method reported previously (Kuttel, et al., 1998). The films produced in this way are composed of large quantities, e.g., up to 0.8 g/d from a single chamber, of aligned nanotubes. The XPS of the specimens indicate a covalently bonded C-N arising from nitrogen doping into the carbon network. The C 1s spectrum presents a main peak at 285.4 eV and a distinct shoulder at 286.9 eV. The former is characteristic of graphitic carbon and the latter indicates that the carbon atoms are bonded by nitrogen. The N 1s peak is located at 400.9 eV, which confirms the presence of nitrogen atoms in a graphitic-like structure (Casanovas, 1996). The presence of nitrogen in individual nanofibres is also detected by spatially resolved electron energy loss spectroscopy (EELS) and the level of nitrogen doping is found to be as high as 10%.

14.8.1 Polymerized Nanobell Structure
The HRTEM images reveal that conventional nanotubes with long cylindrical structures are not present in the samples. Instead, a bamboo-like structure is observed from these nanofibers (Fig. 14.16(a)). A similar morphology was previously observed from pure carbon fibers prepared under catalytic growth conditions (Audier, et al., 1981). However, the latter, which forms during a high-temperature treatment, has a very thin conical top and the surface of the fibers is not smooth. In comparative experiments, carbon nanotubes prepared from pure CH4 without using N2 under exactly the same conditions invariably form elongated cylindrical structures and no bamboo-like morphology is observed. Closer examination of the HRTEM images indicates that the nitrogen-doped carbon nanofibers are actually linearly polymerised short nanotubes with one end sealed and another open, and designated carbon nanobells (CNBs) (Fig. 14.16(b)). The atomic layers in the walls of the CNBs are parallel to each other with an interplanar spacing of about 0.34 nm, which is similar to that of multiwall carbon nanotubes. Unlike carbon nanotubes, however, the diameter of a nanobell increases continuously from the top to the bottom, i.e., no part of the walls is parallel to the axis of the nanobell. The formation of such a conical structure is probably due to the presence of an excess of pentagons near the upper (or closed) end of the bell, but in addition, it seems apparent that all the graphitic sheets stop growing when their open edges extend to a certain distance from the center of the catalytic particles. The detailed mechanism for this is by no means clear, but since the metal nanoparticles serve only as initial nucleation centers on the substrate, and all individual nanobells are completely self-contained throughout the entire length of the nanofiber, it must be dependent on the presence of nitrogen in the gas mixture, as confirmed by experimental findings. As a result of being built up of nanobells, the outer longitudinal surface of the nanofiber is no longer terminated with a single graphitic
171

layer as in the normal carbon nanotubes, although it looks just as smooth in the SEM or the low magnification TEM images. In the nanofibers built up from nanotubes, however, the greater part of the fiber surface consists of apparently open ends of the graphitic sheets! This novel surface structure undoubtedly plays a major part in determining the unusual physical properties of these nanofibers.
Figure 14.16 (a) HRTEM images of a single fiber showing the polymerized carbon nanobells. (b) The detailed structure of the nanobells.

Many nanofibers have larger diameters, i.e., in a range of 100–200 nm. The structures of these nanofibers seem to be much more complicated. However, the HRTEM images from these nanofibers again indicate the same principle of polymerisation of nanotubes. Apart from the differences in diameter between the thin and thick nanofibers, the wall thickness of the latter type is often greatly reduced and the nanobells are apparently much less rigidly arranged, often displaying distortions and various defects. Nevertheless, the surface atomic structure of these thick nanofibers, which is of main interest, is the same as that of the fine ones. Both types of nanofibers are straight and lack the helical morphology observed in the previously reported C-N nanofibers: they can therefore be aligned easily in thin films and are consequently suitable for large area field emission experiments.

14.8.2 Chemical Separation and Application
These nanofibers can be used as precursors to produce isolated nanobells, which may serve as the basis of nanoreactors, allowing catalytic particles to be loaded. In addition, these nanobells can be regarded as unclosed multiwall fullerenes and may be used to store various large molecules or clusters of metal atoms followed by closing the open ends in a suitable treatment (Zhou, et al., 2000).
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It is known that direct control of the length of carbon nanotubes in a nanometer scale is extremely difficult. Therefore, the nanofibers containing polymerised nanobells are good precursors for producing short nanotubes. The open edge of the nanobells is a highly reactive chemical center. Several methods for the oxidation and opening of carbon nanotubes have now been published (Tsang, et al., 1994), and of the solution methods acidified potassium permanganate seems to offer the best results. We therefore used this method to corrode the open edges of the nanobells, and completely isolated nanobells are eventually obtained (Zhou, et al., 2000). It is found that the reaction time is crucial, as when the time is too short the nanobells are still connected to each other in the nanofibres. Conversely, if the sample is over-reacted (e.g., longer than 4 days), the nanobells are mostly damaged.

14.8.3 Wall-Side Field Emission Mechanism
The typical field electron emission characteristics, i.e., both the spatial distribution of emission sites and the total emission current-voltage (I-V) characteristic of the specimens, are investigated with the transparent anode imaging technique. A quite low threshold field of 1.0 V/mm is observed, which is considerably lower than the value of 1.5 V/mm from pure multiwall carbon nanotubes reported by Kuttel et al. (Kuttel, et al., 1998). The highest current density detected from the specimens is about 200 mA/cm2 for an applied field of 5–6 V/mm. The relative fluctuation from a specimen at a current density of 150 mA/cm2 is 1.3% during a test period of 200 s and no significant degradation of the current density is observed over 100 h. Figure 14.17(a) shows a typical spatial distribution of the emission sites on a piece of film, which has an irregular shape as shown in Fig. 14.17(b). Apart from the strong emission sites appearing as white pattern in the picture, a number of individual dots corresponding to "weak" sites are also observed. The overall uniformity of emission is demonstrated by the similarity between the image and the real specimen shape.
Figure 14.17 (a) The spatial distribution of emission sites of a nanofiber film. (b) The shape of the film. (c) A multisegments microscopic emission image. (d) A single-segment microscopic emission image.

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Further studies concentrating on the "weak" sites show that the field emission pattern consisted of a number of bright segments of circles (Fig. 14.17(c)). The images having a single segment, as shown in Fig. 14.17(d), can be obtained at relatively low gap fields. Some moon-like segments rotated during the observation to other parts of circles with the diameters matching the size of the nanofibers. Consequently, the patterns consisting of full circular bright spots can often be observed as time progresses. Saito et al. obtained the field emission patterns from both close-top and open-top multiwall carbon nanotubes (Saito, et al., 1997). Their images show full bright rings due to the electron emission from the circular edges of the graphite layers. In our samples, however, whether before or after undergoing an emission test, neither graphite flakes nor open-top nanofibers are detected. The only possible mechanism of formation of these segment images is therefore that the electrons are emitted from the sides of the nanofibers, which are not standing exactly parallel to the applied field. More precisely, it appears highly probable that the emission sites are the open ends of the nanobells.

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1998).. 1998) and also probably results from uneven ion bombardment during nucleation period.. Weng-Sieh. Suenaha. 2000). et al.18 SEM image of large-scale oriented BCN nanofibers. 14.1 Microstructure and Composition Figure 14. et al. The growth time of this sample is 20 min.. et al. Figure 14. pyrolysis (Terrones. et al. etc.9 Highly Oriented Boron Carbonitride Nanofibers Different experimental methods. 1996. these studies only present some nanotubes/nanofibers in random orientation. the site distribution of the nanofibers is not quite uniform. The diameters of BCN tubes are in the range of 200–400 nm.. et al. et al. and the average density of the nanofibers is estimated to be about 108/mm2. 1996. et al. 1995. 175 . 1997). Redlich. et al. The large-area highly oriented BCN nanofibers are first synthesized directly on polycrystalline nickel substrates by bias-HFCVD (Bai. tangly distribution and low yields. Microsize BCN rods are also reported by HFCVD (Yu. Sen. which hamper both the fundamental and the applied studies of the BCN nanotubes... 1994.. The BCN nanofibers are obviously perpendicular to the substrate surface and are of more or less similar height. However.14. have been adopted to grow BCN nanotubes.. which is due to the insufficiency of nickel as catalyist along the grain boundaries of polycrystalline nickel substrate (Huang..9. such as electric arc discharge (Stepham.. 1997). et al. et al. 1998). and laser ablation (Zhang. However..18 shows the well-aligned BCN nanofibers on the nickel substrate.

2000). A growth mechanism for pure carbon tubular structures is given on catalytically active Ni{110} (Kuang. It definitely shows that the nanofiber is a multiwalled centrally hollow tube. a distinct feature of the BCN fibers is that many small graphitic spines stand on the surface of the fibers. the chemical composition of this BCN nanotube can be determined quantitatively from EELS. and the corresponding maximum emission current density is about 120 mA/cm2. The analysis of the data reveals that the ternary BCN compound is B1. and 401 eV. we show that the composition of the BCN nanofibers can be controlled artificially (Bai.92 mA is obtained at an electric field of 8. Figure 14. which is regarded as the threshold electric field (Fig. Using a method described by Egerton (Egerton.HRTEM is used to determine the interior and wall structures of the BCN nanofibers. These results show that the BCN nanofibers have lower threshold electric field and higher emission current than that of 176 . The EELS measurements of K-edge absorption for B.64N0. C.0C0. Each core edge fine structure consists of a sharp π* peak and a well resolved σ* band characteristic of sp2 hybridization.19 EELS spectrum of a BCN nanofiber. This attests that the three atomic species are arranged in planes of graphite-like hexagonal rings. A maximum emission current of 0.. 1986). et al.26 nA can be detected at the applied electric field intensity of 1. However.19 shows the local EELS spectrum of a nanofiber. which correspond to the characteristic K-shell ionization edges of B. respectively.8 V/µm. 2000). and N are used to determine the chemical composition of nanofibers. 284.20). An emission current of 0. et al. Figure 14. Furthermore.. and N.60. 14. we have studied the field emission behavior of the BCN nanofibers.6 V/µm. C.9. The typical ionization edges are observed at about 188.2 Field Electron Emission Furthermore. 14. The BCN nanofibers in the present work have very similar structures to those of large CN nanofibers discussed in above section. making the fibers cactus-like.

As elaborated earlier. the physics/materials science community has been witnessing a flood of studies. and technologically important material system.4. which is not only important for basic research but also has the potential for industrial applications.7.20 Field emission current vs. challenging. 14. 177 . our ever-increasing understanding of this class of systems has been greatly facilitated by the use of modern growth and analysis technologies and also by a comparison of theoretical calculations. which specifically address the novel formation mechanism as well as their physical and chemical properties of these nanomaterials. Figure 14. applied electric field of the BCN film.10 Conclusions The covalently bonded nanomaterials from light-element composites are an interesting. The field emission properties can be improved by adjusting the composition of the BCN nanofibers.BCN films reported in Section 14. Over the last decade.

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15,Self Assembled Ordered Nanostructures 15.1 Ordered Self-Assembled Nanocrystals
Self-assembly nanostructure is a new form of material with fundamental interest and potential technological applications (Brus, 1991; Wang, et al., 1991; Fendler, et al., 1995; Alivisatos, 1996a, 1996b; Pileni, 1997; Wang, 1998a; Collier, et al., 1998; Brinker, et al., 1999; Ying, et al., 1999). The rapid expansion of research work in this area is driven by the need to further miniaturize electronic components. Another reason is that, in nanoscale, materials properties are quite different from bulks and they are strongly size-dependent. It is possible to process materials which can be tuned via size control to achieve specific functionality. In nanocrystals, the effect from the surface is comparable in some cases to the chemical composition in influencing the chemical, electronic, magnetic and optical behaviors. In nanocrystal self-assembled structures, each individual nanocrystal is the fundamental building unit and it serves as an "artificial atom" for constructing the ordered structure. The analogy of a nanocrystal with an atom is obvious. If the size of nanocrystals is below 10 nm, the energy levels of each individual nanocrystal can be discrete, as in the case of atoms. The energy level spacing and other "atomic" properties can be adjusted by changing the size of the nanocrystals, in contrast to those of the atoms. Size and shape controlled nanocrystals can be viewed as molecular matter with specific shape and electronic structure, and a self-assembly of the nanocrystals can form "nanocrystal solids" with translation and even orientation order. Based on this idea, several kinds (semiconductors, metals, and oxides) of nanocrystal molecules have been successfully synthesized recently, including CdSe (Murray, et al., 1993, 1995; Braun, et al., 1996; Shenton, et al., 1997), InP (Guzelian, et al., 1996), CdS (Hu, et al., 1998), Au (Whetten, et al., 1996; Andres, et al., 1996; Kiely, et al., 1998), Ag (Harfenist, et al., 1996, 1997; Collier, et al., 1997), Pt (Provencio, et al., 1998), Co (Sun, et al., 1999; Yin and Wang, 1999; Petit, et al., 1998), Ni (Sun, et al., 1999), TiO2 (Moritz, et al., 1997), CoO (Yin and Wang, 1997a, b, 1999a), and Fe2O3 (Bentzon, et al., 1989), etc.. At nanoscale, not only the physical properties, but also the chemical properties of materials have been profoundly changed. The huge surface area of each bare nanocrystal suggests that nanocrystals are very reactive, thus, surfactant molecules are needed to cap and stabilize the surfaces of nanocrystals. In the evaporation processing method, for instance, if no surfactant is applied, the freshly made gold nanocrystals coalescence with one another to form heavily twinned larger nanocrystals, but if the surfactant molecules are applied into the reaction chamber, gold nanocrystals can keep the size and shape. After an inorganic nanocrystal is coated with a densely packed monolayer of surfactant molecules, the surface of nanocrystals becomes hydrophobic, and this kind of nanocrystal-surfactant combination is soluble in non-polar solvents and suspend in the solution, forming stable colloids. After the solvent is evaporated or removed, the passivated nanocrystals rearrange themselves to form assemblies instead of fusing together, because they are separated by a thin layer of molecules. Due to the existence of the passivation molecules, the aggregates can be re-dissolved in suitable solutions. If the size of nanocrystals is monodispersive, ordered self-assembly of nanocrystals will be formed, just like the crystallization from solution. The schematic illustration of a typical monolayered nanocrystal self-assembly is shown in Fig. 15.1. The ordered self-assembled nanocrystals of silver are shown in Fig. 15.2.

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Figure 15.1 Schematic illustration of the self-assembled nanocrystals. To form ordered self-assembly, several conditions need to be met: the nanocrystals should be monodispersive; the surfactant molecules should be strong enough to separate the individual nanocrystals; and the drying rate should be so slow that the nanocrystals can move to the suitable positions. The above plot is 2-D assembly of faceted nanocrystals, and the bottom one is assembly of non-faceted nanocrystals.

Figure 15.2 Ordered self-assemblies of silver nanocryastals. The nanocrystals are processed by a vertical aerosol method and later size-selected.

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In summary, due to the capping monolayer of molecules, nanocrystals are held together mainly by van der Waals forces. Three requirements need to be met to make ordered self-assembly of nanocrystals: (1) building blocks (monodispersive nanocrystals); (2) passivation layers (suitable surfactants and solutions); and (3) a slow drying rate to allow diffusion of the passivated nanocrystals in solution to find their equilibrium position. If the drying rate is too high, the disordered arrangement of nanocrystal self-assembly will form, just like a rapid quenching can lead to amorphous phase during solidification. In the following sections, we will first discuss the processing methods, then the characterization method, and the uniqueness of self-assembled nanostructures. Finally, the future directions are also discussed.

15.1.1 Processing of Nanocrystals for Self-Assembly
The controlled fabrication of very small structures at scales beyond the current limits of lithographic techniques is a technological goal of great practical and fundamental interest. Important progress has been made over the past few years in the preparation of ordered ensembles of metal and semiconductor nanocrystals. Processing of nanocrystals can be dated back to Faraday's time, though at that time gold nanocrystals could not been physically observed. Many methods have been developed to process different kinds of nanocrystals, single phase or compounds. Here only the methods that can produce or have the potential to produce monodispersive nanocrystals or quasi monodispersive nanocrystals will be discussed.

15.1.1.1 Metallic Nanocrystals (Au, Ag, Co, Ni, Pt, etc.)
The processing methods of metal nanocrystals can be roughly divided into two groups: chemical methods and physical methods. The reduction of metal ions in solution is the most popular and economical one. Though evaporation of metals at high temperature can also yield metal nanoclusters, this method is not suitable for compounds because of potential problems such as thermal decomposition and possible oxidation. Gold nanocrystals can be prepared either by an aerosol method or the chemistry method. In the chemistry route, Farady (1857) first used the two-phase method to prepare stable colloidal metal nanocrystals, in which he reduced an aqueous gold salt with phosphorus in carbon disulfide and obtained a ruby colored aqueous solution of dispersed gold nanoparticles. In a typical process (Whetten, et al., 1996), the gold nanoparticles growing from metal ions AuCl-4 are reduced at the oil-water interface in the presence of an alkylthiolate surfactant (SR, where R=n-CnH2n+1, n=4, 6, 8, 12,...) and a reducing agent, sodium borohydride. The strategy used here is to finish processing of gold nanocrystals and attaching surfactant molecules in one step. By an extended exposure to excess reducing agent defective structures initially formed can be etched away. The aerosol method can also be used to process monodispersive metal nanocrystals. From the flow direction of the aerosol in the furnace, the setup can have two different types: one is horizontal (Andres, et al., 1996), the other is vertical (Whetten, et al., 1996). Gold atoms are evaporated first from a carbon crucible in a resistively heated carbon tube, which are entrained in He and induced to condense into nanoclusters by mixing the hot flow from the oven with a room temperature stream of helium. Controlling conditions in the oven and the flow downstream from the oven controls the mean cluster size. The clusters are molten and
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recrystallized while still in the gas phase. They are scrubbed from the gas phase by contact with a mist of organic solvent containing 1-dodecanethiol and collected as a stable colloidal suspension. In order to ensure that all of the clusters are single crystalline, a dilute aerosol stream of clusters suspended in inert gas is passed through 1 m long tube in which the clusters are first heated above their melting temperature and then cooled to room temperature. Treating small gold clusters in this way transforms them into face-centered-cubic (f.c.c.) single crystals. Platinum nanocrystals can also be processed by reduction of platinum ions with the presence of capping materials (Ahmadi, et al., 1996). For example, the shapes and sizes of platinum nanoparticles are controlled by changes in the ratio of the concentration of the capping polymer material (sodium polyacrylate) to the concentration of the platinum ions (from K2PtCl4) used in the reductive synthesis of colloidal particles in solution at room temperature. In this method, hydrogen gas is bubbled at a high flow rate through the solution. Tetrahedral, cubic, irregular-prismatic, icosahedral, and cubo-octahedral particle shapes were observed (Wang, et al., 1997), whose distribution was dependent on the concentration ratio of the capping polymer material to the platinum cation. The magnetic nanocrystals like iron, cobalt, and nickel can be processed by the decomposition of metal carbonyl in organic solution. It was noticed very early that thermal decomposition of metal carbonyl in organic solution (with surfactant) often led to metal nanocrystals with a very narrow size distribution (Thomas, et al., 1966; Papiper, et al., 1983). Thermal decomposition of cobalt carbonyl in different kinds of solution (toluene, xylene, etc.) with different kinds of long C-H chains and strong ionic group (sulfonate) surfactant have been systematically studied. Ordered magnetic nanocrystal self-assembly was processed (Sun, et al., 1999) using the traditional reverse micelle technique. Choosing the cationic surfactant, didodecryld ammonium bromide (DDAB) with toluene as a binary system, DDAB as the reducing agent, the Co2+ from CoCl2 can be reduced to form cobalt nanocrystals with the assistance of PR3 (R=n-C4H9, n-C8H17) as the capping material.

15.1.1.2 Semiconductor Nanocrystals (CdSe, CdTe, etc.)
From the technological point of view, semiconductor nanocrystals are potentially important and useful. The band structure of semiconductor nanocrystals is quite different from that of the bulk material (Fig. 15.3). Nanocrystals have discrete excited electronic states and an increased band-gap in comparison to the bulk semiconductor materials. The smaller is the size, the bigger is the difference. The difference can be easily differentiated by optical absorption spectroscopy. But for indirect bandgap semiconductors like silicon and rock-salt CdSe, the optical spectra are continuous, though the individual valence and conduction band eigenstates are discrete. The bandgap is tunable via controlling nanocrystal size, providing an effective way of adjusting the electronic structure in addition to controlling particle chemistry.
Figure 15.3 Schematic comparison of the band structure and electronic states of semiconductor nanocrystals and bulk semiconductor (Brus, 1991).

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4. et al. In 1988.4 (a) The emission spectra of several surfactant-coated monodispersive semiconductor nanocrystals. the nanocrystals behave fundamentally as indirect bandgap materials with low oscillator strength.1. principally as a result of efficient oxide passivation.. Measured quantum yields are as high as 50% at low temperature. Despite a 0. CdSe is still the most intensively studied semiconductor nanocrystals (Nirmal. et al. And up to now... Brus's group at Bell Lab first reported a process for synthesis of pure and stable organic capped CdSe nanocrystals using an inverse micelle method (Steigerwald. 1999).The most typical example is silicon nanocrystals. more effort as concentrated on the semiconductor compound (VI-II and V-III type) nanocrystals.3). 3. 1993).. 1998. Size-selective precipitation and size-exclusion chromatography clearly separate the silicon nanocrystals from larger crystallites and aggregates and provide direct evidence for quantum confinement in luminescence. 1996. For the indirect bandgap semiconductors such as silicon and rock-salt CdSe nanocrystals the optical absorption spectrum is continuous.4. 1988).6 and 187 . This is because many overlapping discrete transitions appear to be present with roughly equal intensity via electron-phonon interaction.. et al. even though the bandgap increases and the conduction band eigenstates are discrete. et al.1. Due to the oxidation on the surface of silicon nanocrystals. Semiconductor nanocrystals have discrete excited electronic states and an increased band gap in comparison with bulk materials (Fig. The dynamics and spectroscopy of silicon nanocrystals that emit at visible wavelengths were analyzed by Wilson (Wilson. 15.9 eV shift of the bandgap to higher energy. the CdSe nanocrystals are nearly monodispersive. et al. The solid lines series represents different sizes of CdSe nanocrystals with diameters of 2. Figure 15. Bruchez. By separating the nucleation stage from the growth stage and the following precipitation process. Tomaselli. 2. 3. The size-dependent emission peaks collected from several monodispersive semiconductor nanocrystals are shown in Fig. 15.

dimers. The general trend for the interparticle interactions in these dispersions can be understood within the framework of a van der Waals core-to-core attractive potential. 1998). one can distinguish three types of dispersions: sterically stabilized dispersions. The self-organization of CdSe nanocrystallites into three-dimensional semiconductor quantum dot superlattices (colloidal crystals) has been demonstrated. 1998). Within these considerations..g. Nanocrystal association. The study also provides information on the interparticle interactions and their dependence on a few relevant parameters.8. 4. and unstable dispersions where strong attractions induce macroscopic aggregation.4.5 and 4. (b) A true-color image of a series of silica-coated core (CdSe)-shell (ZnS or CdS) nanocrystal probes in aqueous buffer. The low polydispersity measured confirmed the high quality of the nanocrystals prepared using a high-temperature solution chemistry route. such as nature of the capping molecules and solvent. to which are superposed effects of cap affinity to the core and to the surrounding solvent. may be caused by a reduction of the cap density as the size is decreased. dispersions thermodynamically stable but governed by weak attractions. and/or aggregation in solutions with strong attractions. This behavior..0.6 and 6.6 nm (from right to left). The properties of CdSe nanocrystal dispersions have been studied by small-angle X-ray scattering method (Mattoussi. all illuminated simultaneously with a handheld ultraviolet lamp (Bruchez. The size and spacing of the dots within the superlattice are controlled with near atomic precision. et al. 3. This control is a result of synthetic advances that produce CdSe nanocrystallites exhibiting monodisperse within the limit of atomic roughness. unexpected for colloidal dispersions. The dash lines series is of InP nanocrystals with diameters of 3. The study also unveiled other features where interactions are reversed from repulsive stabilizing to attractive as the particle size is decreased.6. The methodology is not limited to semiconductor quantum dots but provides general procedures for the preparation and characterization of ordered structures of nanocrystallites from a variety of materials.0 nm. et al.6 nm. can be observed. in dispersions characterized by weakly attractive interactions. as anticipated from optical data.. e. The study can provide accurate measures of the nanocrystal size and size distribution. It was shown spectroscopically that electronic energy transfer in close-packed CdSe quantum-dot (QD) solids 188 . The dotted lines series is of InAs nanocrystals with diameters of 2. 3.

7 nm to 15 nm in diameter (σ<4. 15. α-Fe2O3.9 nm.1 Selection of Monodispersive Nanocrystals Whatever processing methods used.5%).2. etc. After drying the colloidal solution. The method used to form these materials is based on controlling the hydrolysis and polycondensation of titanium alkoxide using organic ligands in order to build and stabilize intermediate building units (slabs). which in turn self-assemble into superlattices. They used time-resolved photoluminescence to study electronic energy transfer in optically thin and clear. the nanocrystal size has a broad distribution even if the processing conditions can be strictly controlled.1.2 nm.) Self-assembling of α-Fe2O3 was first achieved by accident. 1996).3 Oxides Nanocrystals (CoO.1.2 Technical Aspects of Self-Assembling 15. In QD solids of single size dots. 1989). Optically clear and thin. A simple method to control the growth of TiO2 nanocrystallites and the formation of nanostructured TiO2-based materials has also been developed. consistent with electronic energy transfer from the small to the large dots. close-packed quantum dot solids were prepared from mixtures of small and large CdSe quantum dots (3. et al. a hexagonal close packing of hematite (α-Fe2O3) nanoparticles (antiferromagnet) formed on the carbon substrate (Bentzon. it was found that the iron nanocrystals have been transformed into iron oxide.. Quenching of the luminescence (lifetime) of the small dots accompanied by enhancement of the luminescence (lifetime) of the large dots is consistent with long-range resonance transfer of electronic excitations from the more electronically confined states of the small dots to the higher excited states of the large dots. Anatase structured TiO2 particles with different sizes and shapes are obtained simply by changing the titanium/cation ratio. a red-shifted and modified emission line shape is consistent with electronic energy transfer within the sample inhomogeneous distribution. the standard deviation is 0.5%).85 and 6. σ<4. Lyophobic colloidal nanocrystals attract each other via the van der Waals force.1.arises from dipole-dipole interdot interactions between proximal dots. et al. The small clusters agglomerate into condensed "snow-ball" structure. The attraction is strong because of the near linear additivity of forces between pairs of unit cells in 189 . The nanocrystals had a very narrow size distribution (in the case of mean particle size 6. they measured quenching of the luminescence (lifetime) of the small dots accompanied by enhancement of the luminescence (lifetime) of the large dots.. Electronic energy transfer between close-packed quantum dots using time resolved photoluminescence has also been demonstrated (Kagan. 15.4 nm). After the ferrofluid of iron nanocrystals was exposed to air for about one month (processed by thermal decomposition of iron carbonyl in the mixture of decalin with oleic acid as the surfactant).1. In mixed QD solids of small and large dots. Dispersive ε-Fe3N fine particles synthesized by a vapor-liquid chemical reaction between Fe(CO)5 and ammonia have shown a narrow size distribution and they can form nicely locally ordered monolayer array. TiO2. close-packed QD solids prepared from CdSe QD samples tunable from 1. So the size selection is very important because sometimes the ideal conditions cannot be obtained.

After the addition of methanol.7 nm CdSe) nanocrystals. it is obvious that the color of the solutions of different sized semiconductor nanocrystals is different. Figure 15. Several solvent/nonsolvent systems can be used to make size selection. 1996). (a) Optical absorption spectrum shows a very broad peak before selection. in which from (a) to (d) the peak becomes sharper. From quantum theory.. With more nonsolvent added.5 An example of size selection of semiconductor ( 3. 1993). (Murray. the smaller the nanocrystals. the light absorption peak becomes sharper and the position shifts from 530 nm to 400 nm.different nanoparticles. (d) Spectrum of the final selected nanocrystals. Large nanoparticles have a higher probability of overcoming the reduced energy barrier and precipitate. After the size selection. for example. hexane/ethanol.. 15. (c) Spectrum after dispersion in 1-butanol. etc.. (b) Spectra after one size selective precipitation from the solution with methanol. the 190 . The addition of the nonsolvent increases the average polarity of the solvent and reduces the energy barrier to flocculation.5 (Murray. Gradual addition of the nonsolvent can produce size-dependent flocculation of the nanocrystal dispersion. the size distribution becomes narrower and narrower. chloroform/methanol. et al. pyridine/hexane. et al. The efficiency of the steric stabilization is strongly dependent on the interaction of the alkyl groups with the solvent. The effect of size selection on CdSe nanocrystals is illustrated in Fig.

the formation of self-assembly is basically random. et al... For example. In addition to CdSe semiconductor nanocrystals. this method has also been successfully applied to gold nanocrystal separation. It is the key to search techniques that can guide and design the required nanostructures. Photocorrosion is also a very useful method to narrow the size distribution of some nanocrystal systems. In the schematic illustration of the process of forming self-assembling nanocrystal rings (Fig. polydispersive CdS nanocrystals can be selected to have an average diameter of 4. et al. Self-assembly of silver nanocrystals forming a ring shape with micron scale diameter is an example.. Analysis of the amount of sulfate ions produced by photocorrosion of quantum-CdS colloids revealed that the number of CdS particles in the colloid decreased with promotion of photocorrosion. 15.9 nm by a sequential irradiation with a monochromatic light whose wavelength was changed step by step from 490 nm to 430 nm in air-saturated sodium hexametaphosphate solution. The shift of the peak means that more and more larger sized nanocrystals have precipitated from the colloidal solution. Figure 15. One point needs to be addressed. 1998)..wider the energy gap compared to that of the bulk. 1997). These wires with a narrow distribution of width (15%—25%) were processed by a Langmuir compression technique. 15.6). suggesting that during the course of photocorrosion process photocorroded CdS particles were agglomerated to give larger particles which were further photocorroded. How the self-assembly forms at a specific area or position on the substrate is a very critical problem for applications. 1997).2.1. in most cases. et al. The 2-D self-assembled nanocrystal wires with width 20 nm to 300 nm was fabricated (Chung. The only difference is that the nanocrystal ring is open in the vertical direction. 191 . which shows the possibility of controlling self-assembling (Ohara. The molar absorption coefficient of CdS particles at the first exciton peak was found to be independent of the particle size (Matsumoto.6 An example of self-assembled silver nanocrystal ring formed by an air-bulb assisted method (Ohara. the process is comparable to the ordinary bubble nucleation in a superheated liquid.2 Controlling the Formation of Ordered Self-Assembly Though 2-D ordered self-assembling of nanocrystals can be processed by choosing different processing parameters. 1996). et al.2 nm with standard deviation was 1. that this method can only be applied to nanoparticles with relatively small polydispersity. but the bubble in the liquid is closed in all directions.

1.. it was 192 . Using the light sensitive substrate and suitable mask. et al.. Kiely.Light-directed nanocrystal self-assembly is also an effective method to control the position of self-assembly of nanocrystals (Vossmeyer. 1997). 1998). et al. 15. 1995.. different kinds of self-assembling patterns can be formed on a substrate. Because the surface-bound amino group can be derivatized to give a thiol therminus. the light directed assembly of CdS. CdSe and other semiconductors or metal nanocrystals is possible.3 Assembling of Nanoparticles with Mixed Sizes/Phases Can the mixture of nanocrystals with different sizes form self-assembling packing? Several recent papers addressed this question (Ohara. First take the simplest situation: the mixture of two monodispersive nanocrystals (A and B) with particle sizes RA and RB. On micron-scale.2. et al.

3 Structure of the Nanocrystal Self-Assembly Periodic packing of nanocrystals is different from 3-D packing of atoms in several aspects. 15.624. It was found that self-assembling is an entropy-driven crystallization process. stable AB2 structure will be formed. So if the size ratio is in a certain range. For 0. and when RA/RB 0. to an excellent approximation atoms are spherical. the sizes of atoms are 193 . Heath et al. thus.. while nanoparticles can be faceted polyhedra. 1995). the 3-D packing of particles can be critically affected by their shapes and sizes.58.458 < RA/RB<0. et al. et al. 1998) 15. First.58.1.. also used polydispersive gold nanocrystals to examine the mechanism of self-assembling (Ohara.482 < RA/RB < 0. Figure 15.482. which agrees well with the micrometric scale colloidal crystals. superlattices can be formed in "binary" systems. the mixture can form stable structure. Secondly. phase separation occurs.7). Can these theories be applied to self-assembling of nanocrystals? The self-assembly of nanoscale bimodal packing was observed (Fig.reported that when 0. (Kiely.7 A monolayer ordered superlattice of thiol-stabilized gold nanocrystals with two distinctive sizes and the particle diameter ratio about 0.

fixed. et al. This has been shown recently by Cleveland et al. UV light absorption can be used to determine the polydispersity of the nanocrystals dispersed in the solution. 15. 1996. After the formation of self-assembling. By examining the diffraction peaks that are extinct in the spectrum one may identify the crystallography of the packing. X-ray diffraction is still the most powerful technique to evaluate the average interparticle distance. 1997b) in determination of decahedral Au nanoclusters with sizes of 1. and in most cases the interatomic distance is fixed. X-ray diffraction (XRD) and transmission electron microscopy are the most common tools for structure analysis. (1997a. atomic bonding is due to the outer shell electrons via ionic. The structure of nanocrystals can be refined by quantitative comparison of the theoretically calculated diffraction spectra for different nanocrystal models with the experimentally observed ones.e. particularly those smaller than 2 nm. X-ray diffraction is a powerful tool for refining the structure of nanoclusters. 15.1.. et al. and it is a unique technique to study the in situ pressure and/or temperature induced phase transformation in nanocrystals (Alivisatos. the ratio of particle size to interparticle distance is adjustable. provided the amount of the sample is sufficient.3. This is the reason that a quantitative analysis of the low-angle diffraction spectrum is rather difficult. shape and even orientation (i. This analysis is based on an assumption that each particle is identical in size. The diffraction spectrum at the high-angle range is directly related to the atomic structure of the nanocrystals. prohibiting the access of X-ray diffraction and HRTEM. 1996). There are many characterization methods can be used to measure the properties of the self-assembly of nanocrystals.. In the stable colloidal solution. The interconnecting between the nanocrystals in the self-assembly can be analyzed by impedance spectroscopy. a fluctuation in the size.2 Crystallography and Orientation Ordering Determined by TEM 194 . thus. 1995)..3.. so that the extinction rules derived from diffraction physics apply. This method applies to metal nanocrystals and semiconductor nanocrystals. Mass spectroscopy is also very powerful for detecting the critical sizes of the smallest nanoclusters that can be synthesized and the magic number of atoms comprising the clusters (Alvarez.9 nm. metallic bonding or the mixture. the same X-ray scattering factor). 1997). In practice. orientation or shape can easily abolish this assumption. et al. their scattering from each can be treated independently. but the sizes of nanoparticles can have a slight variation although their size distribution is very narrow.7–1. Murray. et al.1 Small-Angle X-ray Diffraction X-ray diffraction is the first choice to examine the formation of crystalline assembling. covalent. however.. If the particles are oriented randomly so that the entire assembly can be treated as a "polycrystalline" specimen composed of nanocrystals with identical structure but random orientations. Nevertheless. while the spectrum at the small angle region is directly associated with the ordered assembling of nanocrystals (Whetten.1. This type of analysis is unique for clusters in which the atoms have not formed a well-defined crystal lattice. while the bonding between nanoparticles is generated by the passivating thiolate surfactant whose length is controllable. Finally. This is a parameter that is likely to determine the 3-D packing of the nanoparticles.

1998b).8(b)) (Wang. 2000). Figure 15. the orientational relationship between the Ag particles and the nanocrystal lattice is 195 . Therefore. along which four {111} and two {100} facets are imaged edge-on.5) nm and their shapes are dominated by tetrahedral (see the projected triangle shapes in Fig. The inset is an HRTEM image showing the [110] projection of the tetrahedral particles. Self-assembly of nanocrystals can be 2-D or 3-D. The unit cell of the NCS is also oriented along [110]s of fcc. Studies of atomic structures of nanoparticles have been described in the chapter concerning transmission electron microscopy (TEM). It is particularly useful if the ordering is short range and/or the amount of the specimen is rather small. et al.8(a) shows a transmission electron microscopy (TEM) image of monolayer assembling of Ag nanocrystals on a carbon substrate. Three-dimensional assembling of nanocrystals can form large size bulk crystalline materials.. The Ag particles have sizes of (4±0. Here we mainly concentrate on the analysis of nanocrystal assemblies. Figure 15. where the 2-D superlattice is apparent. 1998a.Transmission electron microscopy is an ideal choice in determination of the symmetry and orientation ordering of the self-assembled nanostructures (Wang. a four-face polyhedron enclosed by {111} facets.8 Monolayer self-assembly of Ag nanocrystals whose shape is dominated by tetrahedral. 15. The Ag nanocrystals have a truncated octahedral shape and they are oriented along the [110] of the Ag atomic lattice in the image.9(a) is a TEM image recorded from an Ag NCS deposited on a carbon substrate. Figure 15.

The nanocrystals are turncated octahedra and they have orientational symmetry.. 1996). Accordingly. 15. in which the nanocrystals are oriented following an assembling principle of face-to-face (Harfenist.[110] [110]s and [001] .9(b)). a structure model for the NCS is built (Fig. 196 .9 (a) [110]s TEM image of a 3-D fcc assembled Ag nanocrystal superlattice. Figure 15. (b) The 3-D fcc self-assembling model of the NCS. et al.

edges or corners. in addition to the carbon density contributed by the interdigitated thiolates passivated on the {100} facets (which are edge-on while viewed along [110]s). For the case shown in Fig. The EF-TEM image acquired using the carbon K edge from a Ag NCS gives an interesting contrast feature (Fig. Ag NCSs are deposited on an amorphous SiOx substrate and the effects from the substrate can be removed by processing the experimental images acquired pre.9. If the electrons which have excited the carbon K ionization edge are selected for forming the image.10 (a) Energy filtered TEM image of the fcc structured Ag NCS recorded using the electrons after exciting the carbon K ionization edge. This model is supported by the image contrast displayed in Fig. 15. the thiolates passivated on the four {111} planes (not edge-on) also contribute to the projected carbon density although the {111} faces are at an angle with the projection direction.5 nm to 2 nm. Figure 15.. With consideration of the resolution of the EF-TEM of 2 nm.and post-edge. 1998c). 15.5 nm chain length of the thiolate molecules used for passivating the Ag nanocrystals. The shortest distance between the face-to-face {100} facets of the two adjacent particles is only 1. and the result is shown in Fig. The EF-TEM was performed for the Ag NCS oriented along [110]s. A direct observation of the thiolates can be provided by the energy-filtered TEM (EF-TEM) (Reimer.3. 15. suggesting that the thiolates are tethered on the faces of the nanocrystals and they are likely to be erected on the surface. From the structural point of view. their 3-D assembling is unavoidably affected by the particle shape. we first construct the [110]s projection of the NCS based on the 3-D model given in Fig.10(b). The projected carbon density between the particles shows a contrast pattern that is the strongest between the A and B types of particles. The EF-TEM relies on the principle of electron energy loss spectroscopy (EELS) and the images (or diffraction patterns) are formed by electrons with specific energy losses. 15. For the nanocrystals A and B assembled by facing the {100} faces. the thiolate molecules tethered on the facets of the nanocrystals are likely to interpenetrate.10(a)). Therefore. providing a direct chemical map of carbon.3 Imaging the Surface Adsorbed Molecules If the nanocrystals can be taken as the building blocks. the molecular bonds tend to align parallell on the facets on which they are tethered. almost equal to the 1. the image contrast is approximately proportional to the thickness projected carbon atoms in the specimen. et al.9(a). corresponding to open channels formed by the thiolate molecules. The thiolate molecules are composed of mainly carbon.1. which is the optimum orientation for imaging thiolate distribution between the particles (Wang. the projected density of the thiolate molecules between particles A and B is expected to be higher than that between A and C (or B and C) if the size of {111} faces is the same as the that of {100} as well as the density of the thiolate passivation is the same on both {111} and {100}.15. Therefore. For this analysis. 1995). 15. forming the interdigitative bonds. Here we illustrate the observation of directional. 15. To interpret this phenomenon.9(b).9(a) indicates there are some white spots in the image. thus the EF-TEM of the carbon K edge can give the distribution of the thiolates around the nanocrystals. one may wonder if the surface adsorbed molecules are distributed on the particle surfaces. showing the distribution of the thiolate molecules around the 197 . interparticle molecular bonds formed by the thiolates. An examination of the image shown in Fig. while the contrast is lower between the A and C or B and C types of particles. the channels formed by the bundled thiolates may not be resolved in this type of image.

4 Properties of the Nanocrystal Self-Assembly 198 .nanocrystals. (b) A model of thiolate distribution on the surfaces of Ag nanocrystals. The orientation of the NCS is [110]s and the 3-D self-assembling model is given in Fig.9(b).1. 15. which supports the interdigitative molecular bonding in the NCS. 15.

it is crucial to understand the bonding between metal nanocrystals and the surfactant molecules.. et al. Electrical conductance through such a superlattice of 3. To make such devices successful. 1996). they are expected to have many interesting properties different from either individual nanocrystals or the bulk materials. assemble them into systems with appreciable uncertainty in their connectivity. It may be feasible to chemically synthesize individual electronic components with less than a 100% yield. deposited on a SiO2 substrate in the gap between two gold contacts and linked by an aryl di-isonitrile [1. 1998). Metal/self-assembled monolayer heterostructured diodes connected by conjugated molecular wire had been made (Zhou. which incorporates a high communication bandwidth that enables it to easily route around defects. Teramac. In situ measurements were conducted on both linear and nonlinear optical properties of 199 . exhibited nonlinear Coulomb charging behavior. et al. and yet it operated 100 times faster than a high-end single-processor workstation for some of its configurations. Heterostructured diode at nanoscale is also an important application. This machine contains about 22000 hardware defects. 1997. was built at Hewlett-Packard Laboratories to investigate a wide range of different computational architectures (Heath. each encapsulated by a monolayer of alkyl thiol molecules. In 1995. The electrical conductance through gold clusters interconnected by aryl dithiol and aryl di-isonitrile molecules has been measured by a scanning tunneling microscope (STM). Markovich. double-ended organic molecules were successfully self-assembled (Andres. 1997). A recent report sheds some light on solving this problem. which was used to measure the current-voltage characteristics of a bare gold cluster deposited on a dithiol SAM grown on a flat Au(111) surface (Andres. Future nanoscale computers may consist of extremely large-configuration memories that are programmed for specific tasks by a tutor that locates and tags the defects in the system... 1996).7 nm-diameter gold clusters. If these conductive conjugated molecular wires can be used to link metal nanocrystals.As discussed above. 4-di(4-isocyanophenylethynyl)-2-ethylbenzene]. Organic interconnects (aryl dithiols or aryl di-isonitriles) displaced the alkyl thiol molecules and covalently linked adjacent clusters in the monolayer to form a 2-D superlattice of metal quantum dots coupled by uniform tunnel junctions. et al. has significant implications for any future nanometer-scale computational paradigm. were cast from a colloidal solution onto a flat substrate to form a close-packed cluster monolayer. close-packed planar arrays of nanometer-diameter metal clusters that are covalently linked to each other by rigid. et al. The big obstacle to making full use of the self-assembled nanocrystals is making a defect-free self-assembly. Gold nanocrystals. The results are in good agreement with semiclassical predictions.. a massively parallel experimental computer. In recent years. The defect-tolerant architecture of Teramac. Electronic transport measurement showed a distinctive rectifying behavior from the asymmetry of molecular heterostructure. the dimension of one diode can be decreased below 10 nm. there have been many research groups trying to explore their special properties.. Other significant progress was made in the property measurement by light absorption and impedance spectroscopy in the ordered self-assembled silver monolayer thin film (Collier. et al. the charging transfer process in and between metal nanocrystals and the relative distance between the nanocrystals.. any one of which could prove fatal to a conventional computer. Due to the unique structure of self-assembling. self-assembling of nanocrystals can be ordered if the processing conditions are optimized. and still create a powerful and reliable data communications network. et al. Clusters with diameters <2 nm exhibited "Coulomb staircase" behavior in conductance at room temperature. 1998).

2) nm.3. or. and the linear reflectance drops precipitously until it matches that of a continuous metallic film. the linear and nonlinear optical properties reveal evidence of both classical and quantum interparticle coupling phenomena. for 1.2 < D/2r < 1. for D/2r<1.2. After excessive compression. For D/2r>1.2 (± 0. a sharp metal/insulator transition was observed. The Langmuir film response is initially an RC equivalent circuit. Markovich. the strong plasma peak vanished (Collier.organically functionalized silver nanocrystal Langmuir monolayers as a continuous function of interparticle separation distance.11.11 (a) The change from insulator connection between thiol capped silver nanocrystals (diameter 3. First.2) nm to 0. 1997. the optical response abides by the classical coupling model. as the separation between the particles in the self-assembly became less than 0. The transition between the metal-like and insulator-like can be summarized using a new parameter D/2r. quantum coupling dominates the trends in the linear and non-linear optical responses. the film is again characterized by the optical properties of near-isolated silver nanocrystals. (b) UV absorption spectra collected in situ as film was compressed. Correlation with the nonlinear optical response is indicated. As the monolayer was compressed from an average separation between the surfaces of the metal cores of 1. the film becomes inductive.5 nm) to metallic connection was demonstrated on the plot of frequency dependent dielectric modulus.3. 1998). in which D is the interparticle separation and r is the radius of the nanocrystal. et al. This transition is reversible: The particles can be re-dissolved back into a colloid.5 (± 0. this is also a good method to handle the self-assembled thin films. large area self-assembled nanocrystal films can be formed on the surface of a Langmuir trough and then transfer red to a suitable substrate so that different kinds of properties can be measured. 15. The results are shown in Fig.. evidence for a sharp insulator-to-metal transition is observed in both optical signals.5 nm. 200 ..6 nm. Practically. The nonlinear optical response abruptly decreases to a nearly constant value. Below 0. More work is required to verify if this general conclusion applies to other metal nanocrystal systems. Figure 15. et al. if the trough barriers are opened.

201 .

in which discrete numbers of gold nanocrystals are organized into spatially defined structures based on Watson-Crick base-pairing interactions.1 nm to 1. whereas smaller core nanoparticles exhibit redox chemical character. we anticipate that their electrochemical. and kinetic properties will.A strategy for the synthesis of "nanocrystal molecules".4 eV to 0. This approach should allow the construction of more complex 2. 1998). But for the diluted solution with dispersed magnetic nanocrystals. (1996). The change in behavior is consistent with new near-infrared spectroscopic data showing an emerging gap between the highest occupied and lowest unoccupied orbitals of 0. thermodynamic. A transition from metal-like double-layer capacitive charging to redox-like charging was observed in electrochemical ensemble Coulomb staircase experiments from solutions of gold nanoparticles of varied core sizes (Chen. Larger area 2-D magnetic nanocrystal self-assembly and the corresponding magnetic properties have also been reported (Sun. Larger cores display Coulomb staircase responses consistent with double-layer charging of metal-electrolyte interfaces. upon further study. If the building block in the self-assembly is magnetic nanocrystals. All these results demonstrate that the interactions between the nanocrystals in a self-assembly influence the magnetic properties. the transition temperature is 105 K. it may aid understanding of other nanophase properties. In the case of semiconductors.. et al. The magnetic measurement showed that broad transition from superparamagnetic to ferromagnetic at 165 K is due to the magnetostatic particle interactions in the close-packed nanocrystal network. and these assemble into dimers and trimers in addition of a complementary single-stranded DNA template. The charging effect of metal nanocrystals in the self-assembly is very important to understand the basic properties of self-assembly. et al. because the staircase behavior is closely related to MPC core electronic energy structure. although differences in fundamental properties reside in the metal-like and molecule-like charging behaviors. some extra magnetic effects may be brought in. Semiconductor nanocrystals can also be used for labeling materials because the band gap can be adjusted by changing the size in the visible light range (Bruchez. The monodisperse gold nanoparticles are stabilized by short-chain alkanethiolate monolayers and have 8 × 103 to 38 × 103 core mass (1. 1998). prove to fit within a common formal representation. Preliminary results showed that the blocking temperature of self-assembled magnetic nanocrystals have some differences from the bulk materials. Finally. were proposed by Alivisatos et al. Stark effect was found very strong at nanoscale. Single-stranded DNA oligonucleotides of defined length and sequence were attached to individual nanocrystals.9 nm in diameter).and 3-D assemblies between organic and inorganic materials. Quantum-confined Stark effect in quantum wells is very useful for optical modulations. et al.8 nm) to 63 K. In addition. 15.. 1999). It was reported that the blocking temperature of 2-D monolayer of cobalt nanocrystal increased from 58 K (for isolated cobalt nanocrystals with an average size of 5.9 eV. such as the metal-insulator transition of silver nanoparticles upon compression. It was predicted that the difference may be even higher in the case of 3-D nanocrystal self-assembly.2 Ordered Self-Assembly of Mesoporous Materials 202 . including a large central gap..

van der Waals force. 1997). Normally. In this thesis.5 nm successfully developed several dozen years ago. these materials can be divided into two groups: ordered pore structure and disordered pore structure. and double length-scale ordered porous structure of SiO2... Zakhidov. the surfactant molecules self-organize into many small micelles in nanoscale into 1-D. 1997). 1992. Scientists at Mobil invented a novel and simple method that can be used to process ordered mesoporous materials. separation membranes and electrodes for energy storage. et al. Sr) MnO3. 1995a. a hydrophilic head group and a long hydrophobic tail group. 1997) have been prepared by this technique. the aerogel method can be used to process the disordered mesoporous materials also with high pore volume percentage (Prakash. three different kinds of porous materials have been prepared: ordered porous polyurethane filter. such as zeolites with pore size less than 1. et al. such as waveguides and optical switches (Wijnhoven and Vos. 2-D or 3-D material's networks with long range order in the liquid mixture.5 nm. It is only very recently that there has been a big step forward in this area. which lowers the connectivity of pores and degrades the mechanical properties. etc. This method is called "supramolecular templating" (Beck. 1998). 1995b). only the ordered mesoporous materials are to be covered. porous (La. which can be used to process positive or negative ordered structure.. et al. Kresge. ordered mesoporous materials can also be processed by self-assembling mechanism through hydrogen bonding. surfactant molecules used as supramolecular template have an asymmetric structure. The large surface area of the porous materials is ideal for catalysis due to the enhanced surface activities.. Further.2. such as catalysis and sensors. using stable colloidal monodispersive template spheres to process the ordered porous materials has attracted a great deal of research interest due to the simplicity and flexibility of the method. with great prospects in electronic devices. 1998. 1998). et al. 1998. The most common templates are silica or polystyrene. and the size of the ordered pores is adjustable by changing the size of the monodispersive spheres. As we all know. graphite (Zakhidov.Preparation of porous materials with low density and large surface area is important for many technological applications. the ordered assembly has a great potential in photonic crystals. But the pore size distribution of the mesoporous materials is very broad. Photonic crystals of tunable frequency band gap are useful for optically activated devices. electrostatic forces. et al. Using a template-assisted technique.. et al. et al. or organic films (Park. From the geometric arrangement of pores.. trying to minimize the interfacial contact 203 . Like ordered self-assembly of nanocrystals. et al.. Holland. 1992). For example. The methods used to make these two kinds of mesoporous materials are quite different. The low density (about 10%—30% of the bulk density) of the material results in very low dielectric constant (Bruinsma. et al. in which synthetic structures are required with modulated dielectric constant at a periodicity of a few hundred nanometers.1 Processing There are many methods available for synthesis of porous materials. After the surfactant and material precursor are mixed. but most of them are inadequate for processing ordered porous structures. 1998)... diamond (Zakhidov. 15. It is easy to form ordered structure after the colloidal solution is dried. it is much easier to make porous media with pore sizes below 1. The controllable pore size and the interconnected channels in the material make it ideal for applications in filtering. Recently. The general accepted definition of mesoporous materials refers to inorganic materials with pore sizes between 2–50 nm. Ordered porous materials of oxides (Velev.

15. 15. Figure 15. 1999) 204 .. 1992). But in the case in which liquid crystal mechanism was proposed. hexagonal.. 15. 15. simple cubic. which is the structure-composition phase diagram of surfactant (CTBA) in water. But in the case of dip-coating. electrostatic charge balance.between the incompatible molecular ends and achieve low-energy status. et al. the skeleton is preserved and a mesoporous material is formed.2. But from Fig. Both of the proposed pathways involve the interaction between the positively charged ammonium head group of the surfactant and the negatively charged inorganic precursors..14.12 (a) The two mechanisms proposed for the formation of ordered mesoporous silica (MCM-41) which was processed by ionic surfactant CTAB or CTAC: liquid-templating mechanism and incorporated mechanism. liquid phase templating mechanism is almost impossible.13. The mechanisms proposed by Mobil scientists are shown in Fig. etc.12(a). It is clearly shown that.12(b). from which CMC criteria cannot be ruled out as a mechanism Fig. The geometry configuration is summarized in Fig. The drying path in the ternary phase diagram is shown in Fig. etc. 15. (Brinker. as the concentration of surfactant increases. et al.12(b). The typical self-assembling structural model includes lamellar. (b) The temperature dependent phase diagram of CTAB and water. face-centered cubic. the concentration of surfactant changes during the drying process. If the material does not collapse. so a micelle rod cannot even be formed during the early stage of self-assembling. 15. (Beck.2 The Formation Mechanisms The formation mechanisms for the ordered mesoporous materials are still in debate. the concentration of surfactant was well below the critical micelle concentration (CMC). The solution with ordered micelle structures can be gelled later at temperature higher than room temperature for several hours or longer after the surfactant molecules are removed by heating or washing. the micelle can self-organize into hexagonal liquid crystals and then to lamellae structure. The most acceptable mechanisms include: liquid crystal mechanism.

point B is the near drying line. Initial surfactant concentration is below critical micelle concentration (CMC). and point C is the composition of dried film. water.Figure 15. (Brinker.. et al. Point A is the initial composition.13 (a) Steady-state film thinning profile during dipcoating of a mixed solution of silica precursor. (b) An approximate path in the ternary phase diagram during dip coating. 1999) 205 . surfactant and alcohol.

(b) Face-centered cubic packing of disperse spheres. (c) Hexagonal structure.14 The possible configurations of liquid crystals: (a) Body-centered cubic packing of disperse spheres. (d) Undulated 206 .Figure 15.

(j) Undulated lamellae with tetragonal symmetry. (l) Hexagonally perforated lamellae with rhombohedral symmetry (Antonietti. (e) Gyroid phase. (g) Im3m phase. (f) Bicontinous double-diamond structure. 207 . (k) Tetragonally perforated lamellae. (i) Planar lamellar structure. 1997). et al. (h) Spongelike structure..cylinders with tetragonal packing.

Even though it seems none of them can solve all of the problems. The distribution coefficient. 1997) 208 . including micelle layer mechanism. (Feng. Functional groups like thiol groups have been successfully introduced onto the pore surface of mesoporous silica as the terminal groups of organic monolayers (Fig. For non-ionic surfactant.2. et al. has been measured as high as 340000. This material can efficiently remove mercury and other heavy metals (such as lead and silver) from contaminated aqueous and organic solutions. the reaction mechanism can be represented as S+ I-. charge density matching mechanism. the favorable structure.Several other mechanisms were proposed. etc. A general form of electrostatic interaction can be used to represent the mechanism: for example. larger structure features up to 30 nm by increasing the molecular weight. 15. The siloxane groups then underwent hydrolysis and ultimately became covalently attached to the substrate and cross-linked to one another. mesoporous Nb2 O5 was processed by forming a covalent bond between the Nb2 (C2 H5 O)5 precursor and an amine temping agent.15 Functional monolayers on the internal surface of mesorporous silica support can remove heavy metal contamination such as mercury from aqueous and organic solutions. non-toxicity. lower decomposition temperature (compared with cationic ammonium the most common surfactant used).3 Applications The applications of mesoporous materials mainly depend on these two properties: (1) the huge surface area. (a) The TEM image shows the preservation of the porous structure after the attachment of functional monolayer. The surface area measurement of silica indicated that the internal connectivity of ordered mesoporous materials is better than disordered. For some special purposes. For non-ionic surfactants. (b) An energy dispersive spectrum shows the sulfur signal from functional monolayer and mercury signal from the contamination in water. the pores need to be interconnected because the closed internal pores are inaccessible to outside by gas or liquid phases. 15. Compared with ionic surfactants. the pore size required. But the surfactant molecules and the inorganic precursor can form hydrogen bonding or covalent bonding.15). Selection of surfactants depends on the compatibility of the precursor. in which S is surfactant head group and I is inorganic precursor. and heating temperature. For example. To use the high surface area in catalytic applications. the polyethylene oxide polymer surfactant has many advantages. [Kd is the amount of adsorbed metal (µg) on 1 g of adsorbing material divided by the metal concentration (µg/L) remaining in the treated waste stream. the form is S0 I0. including low cost. the internal surface should be activated for the functional groups to be attached. for ionic surfactant.] Figure 15. one point is widely accepted that the self-assembly is formed due to the electrostatic interaction between the inorganic precursor and the surfactant head. This is easy to be understood for ionic surfactants. and excellent interfacial stability. Kd. The hydrocarbon chains aggregated and formed close-packed arrays on the substrate.. (2) the porous structure (low dielectric constant). there are no positively and negatively charged species.

in contrast to milli. displays and chemical sensors. Recently. Especially.Another useful area of mesoporous materials is for catalytic applications. the large pore size can be used to fix large active complexes which are out of reach of zeolites. This process can be easily adapted to make silicon-based light-emitting diodes. crystalline linear polyethylene nanofibers (diameter 30 nm to 50 nm) were grown from the pores of the internal surface of mesoporous silica by polymerization of ethylene (Kageyama..or microsecond lifetimes for porous silicon and nanocrystalline silicon (Dago.. et al. The accessible internal surface area can be considered approximately proportional to the catalytic activity. 209 . For example. thus controlling their properties. a simple method was developed to process silicon nanocrystals with size 1 nm in the nanopores of hexagonal mesoporous silica free-standing films. The whole film displayed strong yellow-orange photoluminescence and nanosecond luminescence lifetimes. optical interconnections. 1999). 1999). Another interesting work is using the nanopores of the mesoporous silica to limit the size of semiconductor clusters. et al.

15. and (b) the torn cross section of the film exhibiting porous interior structure. Polyurethane was infiltrated into the space between polystyrene spheres (PSS). In Fig. There has been a great deal of research work on the application of so-called "nanoglass" processed by xerogel method.15 shows the application of nanoporous silica as a low-dielectric material and very good gap-filling property. The sample was put into SEM for observation after coating with a thin layer of gold to minimize charging effect.16 Scanning electron microscopy images of an ordered porous polymer showing (a) the top as-prepared surface. 210 . Figure 15. The film is continuous without crack.For low dielectric applications. These are the unique characteristics of the film.16 (b). Continuous. with continuous and fairly smooth morphology. the sample was put into a beaker with pure toluene for 24 h to dissolve the PSS. Figure 15. flexible and transparent filters can be processed as well. Then the composites of PSS and polyurethane were gelled at 80°C for 24 h. and it has extremely high mechanical flexibility and is optically transparent. 15. After the gellation.16 (a). The thickness of the filter can be controlled by the mold and the amount of polyurethane used in the experiment. the plane view of the pore films showed that the pores are ordered and from the cross section of the torn surface shown in Fig. it is the total volume of pores in the film rather than the internal connectivity that influences the dielectric constant of the porous media.

211 .

66Sr0.33MnO3 were 0. Nb2O5 (Sun.. SEM image clearly reveals the formation of the porous structure (Fig. 1998). and MnxOy (Tian. et al.66Sr0.. and the average grain size calculated from the peak width at half maximum using the Scherr equation is about 12 nm.17(d)) and EDS microanalysis also proved that the composition and crystal structure agreed well with perovskite La0. 1998). electrodes in fuel cells and mixed valence catalysts. et al. Ta2O5 (Antonelli.17 (a) SEM image of the porous La1-xSrxMnO3 structure prepared by the template-assisted technique. Sr)MnO3 is an example. et al. X-ray diffraction showed that the structure was La1-xSrxMnO3 perovskite (Fig. showing the perovskite structure. et al. After the solution was infiltrated into the template and gelled at 80°C for several days... 1999). (c) A bright-field TEM image showing the average grain size is about 10 nm—20 nm.. there is less ordering possibly due to the large mass change and volume shrinkage during heat treatment. 1996b)..4 Mesoporous Materials of Transition Metal Oxides Due to several oxidation states of transition metal ions. 1997). The precursor used to prepare porous La0.2. the solar cell using mesoporous titania (anatase phase) as electrode has a high conversion efficiency (as high as 33%) from photons to electric current.. 15. mesoporous transition metal oxides have many important applications like gas separation membranes. SnO2 (Severin. Electron diffraction (Fig. This is the basis of functional and smart materials (Wang and Kang. 15.17(b)).33MnO3. 1995). Though the pore structure is visible. ReO2 (Herrmann. It was shown that this precursor is a stable. and manganese (II) acetate tetrahydrate (Yang. 1995. 1996a). strontium acetate. Froba.15. 1997).. et al. TiO2 doped with Co (Yin and Wang. (d) An electron diffraction pattern from the particles proving the perovskite structure. the sample was put into an oven at 600°C for 5 h to remove the PSS and transform the gellation into mixed transition metal oxides. (b) An X-ray diffraction spectrum of the La1-xSrxMnO3 powder. et al. TiO2 (Antonelli.03 mol water (with 25% acetic acid) solution of lanthanum acetate hydrate. For example. Figure 15. et al. 212 . clear solution. 1997) have been successfully synthesized. 1998). et al. HfO2 (Liu. et al. 15. The synthesis of (La.17(a)). ZrO2 (Antonelli.. in agreement with the measurements from a TEM image (Fig. 1999b). et al..17(c)). 15.

We have combined the two types of porosities into a new silica structure that has ordering and porosity on two length scales. the ordered assembly of hollow structures of polyurethane and transition metal oxide can be processed by the template-assisted technique. These structures are ordered on the length scale of the template spheres and the pore sizes are in submicron to micron range. This is a second order porous structure. in which the porosity is created by the co-polymer. In fact. one is at the scale 213 . ordered mesoporous silica with much smaller pore sizes in nanoscale range (< 30 nm). which is formed in a single process. A hierarchically ordered material is introduced by combining the ordering at different length scales. Alternatively. has also been processed. produced deliberately by introducing surfactant. Here.3 Hierarchically Structured Nanomaterials The last few sections were focused on the self-assembly of ordered structures at one length scale.15. hierarchical ordering is very common in co-polymer structures. we call this a first order porous structure. As discussed above.

15. and the other is the nanocavities created by self-assembled molecular co-polymers (Yin and Wang. tetraethoxysiliane (TEOS). The material processed without the surfactant co-polymer has porosity only in the length scale of the PSS.18). Finally.of hollow spheres created by a template of polystyrene. 1992).5) nm. et al. after the template was dried. 1999c). Secondly.5 mm and the drying process in air took about 10 h. exhibiting ordering in two length scales: close-packed hollow spheres ( 120 nm) and self-organized nanocavities (4–5 nm). In a typical synthesis process. The ordering at the two length scales is revealed by TEM (Fig. 214 . 40 mL solution was put in a perpendicular open-end glass tube with inner diameter of 1.18 Transmission electron microscopy image of the porous silica.. TEM images and their Fourier transforms have shown that the packing of the hollow spheres has the hexagonal close-packed (hcp) (αh = (120±8) nm) and the face-centered cubic (fcc) (αc = (175±10) nm) structures. the silica precursor. smaller than the size of the PS due to volume shrinkage.. forming the ordered template of PS. 1998). It has been demonstrated that the pore brought in by non-ionic co-polymer surfactant is larger than that reported previously by using ionic surfactant (Kresge. after the precursor was dried slowly at room temperature. The size of the hollow spheres is (120±8) nm. et al. annealing of the template at 450°C for 5 h resulted in the simultaneous formation of the ordered porosity at double length-scales. Figure 15. and a surfactant co-polymer were infiltrated into the space between the PSS in the ordered template (Zhao. The nanocavities formed in the walls of the shells have sizes of 4–5 nm and the interpore distance is (8±1. The structure is stable to temperatures as high as 500°C.

15. Synthesis of new materials using self-assembly is a new approach that has the potential of producing high quality. ordered mesoporous nanostructured materials. and hierarchically ordered 215 . This chapter reviewed the current status of the ordered self-assembled nanocrystals.4 Summary Self-assembling process is fundamental in biological systems in nature. large quantity and chemically and structurally controlled new materials.

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. chemical industry. The drugs are immobilized on the outer membrane and delivered to the targeted sites which recognize the membrane structures on the ceramic particles.2 Nanophase Materials in Environmental and Health Sciences 16.2 Diagonosis 221 . Conway. et al. including nanoporous carbon and conducting oxide materials (Delnick and Tomkiewicz. The successful design and synthesis of next generation electrode materials depend on the manipulation of the electrochemical potential at the atomic level and on the enhanced charge storage and transfer through nanostructural engineering (Zheng and Jow. many nanoscale electrode materials have been investigated. Molecularly Organized nanostructural Materials 16. Recently carbon nanotubes have been investigated for efficient hydrogen storage (Chen.2. 1991). al. 1997. 1995). These opportunities can be illustrated by the following examples.1. et al.1. et al. Chambers. 1994). Nanoparticulate drug delivery systems are among the latest entry into the drug delivery arena (Hnatyszyn. 16.. 1996. 16.1..1 Introduction As discussed in other chapters of this book. 1998). 1999).2. In order to improve the energy density and power density for batteries and capacitors. or other cell-specific ligands. great opportunities in energy storage and conversion. The ceramic particles are coated with tightly adsorbed phospholipid membranes derived from cell structures and viral membranes. Such materials may have potential use in high-density rechargeable batteries and fuel cells. and to reduce environmental pollution caused by energy consumption. However. quantum computation. and nanoscale instrumentation.1 Nanostructural Materials in Energy Sciences There has been intensive research in developing alternative energy devices to increase the efficiency of energy storage and delivery. environmental and health sciences have just emerged in the last few years.. carbon nanotubes can store up to 67 wt% hydrogen (Dillonet. The ceramic particles can be made of calcium phosphate. The nanoparticles are either polymeric or ceramic in nature.16. Alkali metal doped carbon nanotubes can store up to 20 wt% hydrogen under ambient pressure and moderate temperature. nanoscale materials and nanotechnology have generated great interest in the area of microelectronic devices.1. a biodegradable mineral existing in natural biological systems. 16.1 Drug Delivery Nanoscale materials are recently beginning to attract interest as emerging technologies for medical diagnosis and treatment. It was found that at low temperature and high pressure.

These materials demonstrated extremely high efficiency in adsorbing a wide range of species. Liu. These DNA coated nanoparticles can be used to detect the sequence of unknown DNA molecules and may offer the advantage of high selectivity and sensitivity. Liu. or Ca10(PO4)6(OH)2).. 1997.3 Functional Selectivity The DNA modified nanoparticles are among many other examples in which the surfaces of the nanoparticles or nanoscale materials are modified with target specific molecules and functional groups. 1996). The bone tissue consists mainly of collagen fibers and an inorganic component calcium hydroxyapatite (HAP. 1998. et al.3 Molecularly Organized Nanostructural Materials There are two general approaches to fabricate the nanoscale materials: gas phase synthesis and solution phase synthesis. Beck and Vartuli. et al. 1998. 1992. 16.. et al.2. and the functionality in the nanocomposite materials.1 Molecularly Directed Nanoscale Materials in Nature There are many examples of sophisticated nanostructural materials that can satisfy the multifunctional needs of biological systems.2. 1992. the nano-colloids will display a different color change as a function of temperature.1. the HAP crystals (20 nm to 40 222 . thus providing easy means of diagnosis. Mercier and Pinnavaia. This approach allows for rational design of molecular sites. 16. 1996) provide an ideal platform to manipulate the surface chemistry of the materials on molecular and nanometer scales. 1996. et al. 1996. 16. 1997. partial complementary... 1998).DNA molecules have been attached to colloidal gold particles to form "DNA specific nano-colloids" (Mirkin. non-complementary to the DNA molecules attached to the particles. Feng. Raman. et al. On the nanometer scale. et al.. et al.. Kresge. This chapter will use several examples to illustrate the different approaches to fabricate both 2-D and 3-D nanoscale materials. the hierarchical structure of calcified bone tissues has been studied for a long time (Katz. One of the new strategies in the solution synthesis is to take advantage of the fundamental molecular interactions between the different species and use these fundamental interactions to direct the scale. 1996). including toxic metals.1.2 Molecularly Directed Nucleation and Growth. and Matrix Mediated Nanocomposites 16. For instance. the structural ordering. Many of these materials are already used or investigated for commercial applications. We call such materials as molecularly organized nanocomposites. Organized monolayers of functional molecules were assembled inside the ordered nanoporosity to form highly functional hybrid materials (Moller and Bein. Depending upon whether the target DNA molecules are complete complementary. The recently developed ordered nanoporous materials based on templated synthesis (Beck..

nm long) are aligned along the collagen fibers.. These approaches allow the formation of either 2-D nanocrystalline films or 3-D nanocomposites. 16. and these soluble macromolecules alone are responsible for nucleation and growth of the inorganic minerals. 1980. The collagen fibers further organize themselves into helical concentric lamellar structures. 1987). as illustrated in Fig.2 Directed Nucleation and Growth of Thin Films Taking the lessons from nature. functionalization.5 µm and 10 nm in thickness.2. This sophisticated microstructure offers the optimum mechanical properties for the bone tissue. 1992). Another widely studied example is the abalone sea shell. as well as the ordering of the crystalline materials. 223 . The aragonite crystals and the soft tissue are 0. et al. et al. respectively (Liu. 1989): (1) The materials are highly organized on nanometer scale. The inner shell (nacre) is made of a lamellar composite of aragonite platelets and organic soft tissue. et al. 1988) are then deposited on the insoluble organic template. An insoluble organic framework (β-chitin layered between glycine and alanine rich proteins) (Weiner and Traub.. functionalized molecules are used to direct the nucleation and growth. 16. 1996). Zaremba. 1995). et al. which are also aligned along the longitudinal direction of the bone tissue. Soluble polyanionic proteins (aspartic and glutamic acids) (Nakahara. and matrix mediated nanocomposites.1: directed nucleation and growth of thin films. whether it is calcite or aragonite (Belcher.. It has been recognized that the mineral nucleation and growth in the nacreous layer of abalone shells are regulated by an organic template structure. Analysis of the crystalline structure of the nacreous layer reveals a hierarchical tiling of twin related aragonite platelets oriented along the c-axis (Liu. and growth of nanophase materials in polymer composites. Cariolu and Morse. (b) In situ swelling. (2) The material synthesis is directed and controlled by organized functional molecules. 1984. It is difficult to have a complete understanding of exactly how the biological systems regulate the growth of such sophisticated nanoscale materials of different phases and different orientations. (3) The materials are highly functional. a hybrid composite material made from calcium carbonate and organic materials (Currey. Sarikaya. Figure 16.1 Two pathways to prepare nanoscale materials utilizing functionalized molecules as directing agents: (a) Formation of functionalized monolayers on a substrate and growth of oriented crystals and films. The limited knowledge on the nucleation and growth of biocrystals provides some insights on how to synthesize tailored nanoscale composites using lessons learned from the biological systems. Weiner. This combination provides optimum strength and toughness. et al. et al. 1983) is first formed as lamellar envelopes. 1992. et al.. The outer layer of the shell consists of oriented columnar calcite crystals to provide strength and hardness to sustain the pressure and protect the living organism. Some of the most important characteristics of biological composites include (Simkiss and Wilbur.. 1996. There are two possible pathways to achieve this goal. not to mention duplicating these materials with synthetic approach...

molecular monolayers can be prepared from organosilanes. Bifunctional molecules containing a hydrophilic head group and a hydrophobic tail group adsorb onto a substrate or an interface as closely packed monolayers. TEM micrographs of a cross-sectioned samples of iron oxyhydroxide (goethite.2(a). the polystyrene substrate was treated in sulfuric acid or in SO3 vapor. et al. phosphate.. FeOOH) films on silicon wafers and polystyrene substrates (Rieke.2. Deposition of the FeOOH film occurred by thermal hydrolysis of the acidified Fe (NO3)3 solutions at 70°C. can be introduced to the head group via proper chemical treatment.2. 16. and carboxylic acid. et al. 16. Before film growth. such as sulfate.2.2. Selected area electron diffraction and X-ray indicated 224 . In Fig. The vinyl groups were converted to sulfonate groups by reacting in sulfur trioxide (SO3) vapor. and the film orientation was controlled by the sulfonate groups. Experimentally. What is striking in Fig. as well as protein molecules.1 Self-assembled Functional Monolayers on Substrate For 2-D thin films.16. Sulfonated monolayers on silicon were prepared by placing wafers into solutions of vinyl-terminated alkyl trichlorosilanes in cyclohexane. The chlorosilane end of the molecule is hydrolyzed and then covalently bonded to the oxide surface and cross-linked to adjacent silanes.2.2 Controlled Nucleation and Growth To illustrate how the crystalline orientation and morphology can be controlled. These functional groups will induce the nucleation of minerals dissolved in the solution. The hydrocarbon tails provide the driving force (van der Waals interaction) for the self-assembly of the molecules into ordered arrays on the substrate. such as Cl3Si(CH2)nX. Different functional groups. The tail group and the head group can be chemically modified to contain functional groups that stimulate the growth of the desired minerals. 1995. 16. 16.. we have used self-assembled bifunctional monolayers to direct nucleation and growth of ceramic materials on a substrate. the film growth rate is low. Similar films were grown on sulfonated polystyrene.2 are the very different microstructures of the same materials under different conditions. Tarasevich. 1996) are shown in Fig.

TEM study revealed that in the commercial magnetic recording tape.that the film has a preferred orientation. which is not a very favorable microstructure for high-density storage. morphology and orientation) can be obtained.2 closely resemble the two morphologies in the abalone shells: layered microstructure in the nacreous layer and the column-like structure in the outer layer. 16. 16. (b) Kinetically oriented films with [001] column-like structures perpendicular to the substrate. The ability to deposit oriented iron phases may lead to the development of high-density magnetic storage materials.2. does not require high-temperature treatment. 1994). The iron hydroxide films shown in Fig. the film on polystyrene was grown with [001] direction perpendicular to the substrate. and medical implants. We can also see uniform fiber-like structures parallel to the substrate surface.. and the column like structures are controlled by growth kinetics. performed in aqueous solutions. We also demonstrated that the desired micro. 16. The synthesis. Such films and coatings have potential applications in magnetic materials. Fiber-like microstructures are vertical with respect to the substrate surfaces. metal.and macrostructural control (including crystalline phase.2(b)). with [001] direction parallel to the substrate. The layered structure is directed by the functional molecules. et al. Figure 16. (a) Controlled nucleation and growth of layered structures with [001] direction parallel to the substrate.3 Application This molecular monolayer approach has been used to prepare iron oxide. and calcium phosphate as coatings on ceramics. titanium oxide. The column-like microstructure is more desirable (Fig. 225 . scratch resistive coatings. and plastic substrates (Bunker. crystal size. the crystals assume a parallel orientation with respect to the tape. tin oxide.2 Two morphologies of FeOOH films on functionalized substrates.2. On the other hand. ultraviolet blockers.

1998.3(a) shows examples of commercial products on which we have successfully applied the controlled coating techniques. (b) Optical transmission of TiO2 films with different thickness (Baskaran. Figure 16.3 (a) Ceramic thin film coatings applied to complicated shapes.. 1998). et al.3(b) shows the UV adsorption spectrum of TiO2 films deposited on commercial light fixtures. As can be seen from the figure. et al. with permission from American Ceramic Society). the optical transmission below 300 nm is reduced to less than 5% by a 90 nm TiO2 coating (Baskaran. 226 . The TiO2 films protect the fixtures and reduce human UV exposure. Otherwise it would be difficult to deposit uniform ceramic films on these complex objects. Figure 16.Another advantage is the ability to uniformly deposit films on complicated shapes. Figure 16..

such 227 . a polymer material. second pathway).3 Matrix Mediated Nanocomposites Three-dimensional nanocomposite materials can be developed based on simultaneous swelling and functionalizing of polymer materials (Fig. In this approach.1.2.16. 16.

Subsequently. At the same time. Figure 16. 228 . SnO2 begins to deposit. The actual layer thickness is more than 5 µm. a SnO2 polystyrene nanocomposite is formed after several days. and the thickness of the functionalized layer decreases. Finally. In the initial stage (30 s).as polystyrene. SnO2 is widely used as gas a sensor material (Williams and Coles. The polymer swells into a microporous material. Figure 16. 1999). is exposed to SO3 vapor or soaked in a liquid solvent. yet efficient technique to make polymer-ceramic nanocomposites. As the reaction proceeds. Finely divided SnO2 in the composite material could potentially increase the sensitivity of the sensing devices. a functionalized layer is over 5 µm in thickness and contains almost no ceramic material. Figure 16.4 shows that when polystyrene was exposed to SO3 vapor for some time. nanophase ceramic materials are nucleated in the functionalized polymer matrix. At the same time. Only part of the layer was observed in TEM due to tearing during sample sectioning. The decrease in the layer thickness is caused by deswelling due to the collapse of the osmotic pressure through the deposition of the mineral phase. Sulfur can be detected from the sulfonate groups by electron energy dispersive (EDS) spectral compositional analysis. with the SnO2 crystals less than 50 nm in size.5 TEM images of the growth process of SnO2 nanocrystals in polystyrene matrix. the active groups on the polystyrene are converted to desired functional groups. such as sulfonate groups.5 shows the time sequences of the growth of tin oxide-polystyrene nanocomposites. Figure 16. and the relative concentration of Sn to S increases.4 TEM image of sulfonated layers in polystyrene. This is a very simple. nanocrystalline SnO2 begins to appear. a swollen layer was formed.

These new particles are generated by significant crystal growth at the free surface. 16. Figure 16. the diffraction rings become less continuous due to the larger crystalline size. especially on the outer layer. Large particles are observed.Longer growth time can lead to the coarsening of the SnO2 particles. In the outer layer in Fig. It is also interesting to notice that at the outmost surface a new morphology with large SnO2 crystals develops after a long time.6. The change in particle size and morphology is also reflected in the selected area diffraction (SAD) patterns. with increased intensity as a function of time.6 TEM image of SnO2 nanocrystals in polystyrene after long growth time. 229 .6. as shown in Fig. 16.

230 .7(a) is the nanocomposite with very fine particles (less than 5 nm).7(b) is the composite with long time aging. Figure 16.Similar iron hydroxide-polystyrene nanocomposites can also be prepared. (a) Amorphous nanocrystals.7. 16.7 TEM images of FeOOH nanocrystals in polystyrene matrix. as shown in Fig. Figure 16. The crystals have grown into needle-like particles. 16. and Fig. (b) Needle-like particles after long growth time.

16. 231 . and orientation can be controlled through molecular directing. These approaches are discussed in the followingsections. morphology. In the last few years it has become possible to further regulate the ordering on the nanometer scale to form more sophisticated nanoporous and nanostructural composite materials.3 Surfactant Directed Hybrid Nanoscale Materials The examples discussed so far have illustrated how the crystalline size.

Kresge. 1992). The ceramic precursors bind to the micellar head groups and further condense into a 3-D ceramic phase. et al. the synthesis and the properties of such materials.16. and there have been many excellent publications related to the fundamental mechanism. The use of block copolymer surfactants further expanded pore size and the possible compositional range.. Since 1992 ordered mesoporous materials have become a very active research area. Schematically (not mechanistically). 16. tunable pore size from 2 nm to 40 nm.3.. 1992.like micellar structure is shown). et al.1 Ordered Nanoporous Materials 16.8. The rod-like micelles further aggregate into ordered hexagonal liquid crystalline structures. 232 . the organic phase can be left behind to give a highly ordered nanocomposite material (Gray. More recently. scientists at Mobil Oil Research successfully synthesized ordered nanoporous mesoporous materials using surfactant liquid crystals as structure directing agents (Beck. Such ordered nanocomposites are difficult to prepare by other synthetic routes. 16. This process will give a unique ordered porous material as shown by the TEM micrograph in Fig. 1998). Afterwards the surfactant molecules can be removed by thermal or chemical means. the templates were extended to include block copolymers (Yang.8 Schematic of the formation of ordered mesoporous materials using surfactant as the directing templates. well-ordered structure. 1997).1.1 Mesoporous Materials In 1992. as illustrated in Fig. and simple preparation methods.. Experimentally the ordered mesoporous materials were prepared by mixing various surfactants with a wide range of ceramic precursors. the surfactant molecules aggregate into micelles (only rod.8. and letting the mixture react under mild hydrothermal conditions. et al. et al.3. This new class of materials is characterized by an extremely uniform pore size distribution. Figure 16.. If a polymeric material is used as the template.

1980). These molecules include surfactant.16.and intra-aggregate forces. v/aolc. ao is the optimal head-group area.. the ao of an ionic surfactant can be effectively decreased by adding salt or counter ions to decrease the electrostatic repulsion between the head group and/or by increasing the temperature. and lc is the critical chain length. v can be effectively increased by adding oil. 1991. For example. and a larger critical packing parameter (>0. The major driving forces for forming well-defined aggregates are the hydrophobic attractions at the hydrocarbon-water interfaces and the hydrophilic ionic or steric repulsion between the head groups. 233 . not a predictive tool. temperature. Vinson. 16. 1991.9 depends on experimental conditions. where v is the volume of the hydrocarbon chains. which mingles with the hydrophobic hydrocarbon tails. the phase diagrams of the surfactants should only be used as a guideline. In order to quantitatively describe the molecular interactions. is proposed. with permission from Academic Press). As shown in Fig. these amphiphilic molecules have two components: a hydrophobic tail group (or segment) and a hydrophilic head group (or segment). Therefore the mixing of a surfactant with ceramic precursors sometimes fundamentally changes the molecular interactions. a small critical packing parameter (<0. Figure 16. 1991). Like the bifunctional molecules discussed earlier. However. Evans and Wennerstrom. et al. copolymers and proteins (Israelachvili.1. Even though the phase behavior of a wide range of surfactants has been investigated (Tiddy. 16.5) favors the formation of a highly curved interface (spherical micelles and rod-like micelles).2 Mechanisms and Pathways The formation of the ordered nanostructure is determined by the fundamental interactions between the molecules with surfactant like properties. A variety of ordered structures can be formed depending on the solution conditions (pH. lipids. 1994. A critical packing parameter larger than unity will produce inverse micelles. or electrolyte concentrations).9. The equilibrium structures are determined by the thermodynamics of the self-assembly process and the inter.9 Packing geometry of surfactant molecules and its relation to the micellar structures (Israelachvili. a critical geometric packing parameter.3. the surfactant geometry shown in Fig.5) favors the formation of flat interfaces (flexible bilayers and planar bilayers).

cubic crystals. inverse micelles. lamellar phases. Using the ordered liquid crystalline structures as the directing templates. or inverse micellar liquid crystals can be formed. rod-like micelles. hexagonally ordered crystals.Depending on the solution composition. a wide range of ordered nanocomposites can 234 . spherical micelles.

the cubic. Firouzi.. et al. such as the cubic. Adding the silicate species caused the formation of silicate encapsulated surfactant micelles and subsequent ordering (Monnier. Attard. In the co-assembly process. rod-like. et al. (2) Co-assembly. 1988). and inverse micelles. Among these. which are desirable in many applications. and the spherical and inverse micelles have been used to prepare nanocrystalline particles. In addition to ordered mesoporous materials.11 Different mechanisms discussed for the formation of mesoporous materials. 1993. Several possible mechanisms and pathways have been discussed in the literature when surfactants are involved in directing the ordered structures. In the pre-assembly process. et al. the surfactants exist as individual micelles or molecules. and the lamellar phase. et al. followed by the ordering process (Antonelli and Ying. Figure 16. 1995). 1996). and lamellar structures have been utilized for preparing ordered mesoporous materials. 1996..10 Different microstructures formed in surfactant systems: six typical micellar structures observed in surfactant solutions.11 illustrates the three main pathways: (1) pre-assembly. 1995). (3) Modified co-assembly (Liu. such as in piezoelectric transducers and pyroelectric detectors (Newnham. Figure 16. (2) co-assembly. Figure 16. with permission from Elsevier). et al. Ordered nanostructural composites consisting of many of the phases have been successfully synthesized (Huo.. the ordered surfactant liquid crystals formed first... the inorganic species were bonded or integrated to the surfactant molecules to form hybrid inorganic amphiphiles. et al. 1994). In the modified co-assembly process. (1) Pre-assembly. et al. and subsequently the silicate ions bonded to the surfactant head group (Dubois. and (3) modified co-assembly. hexagonal. and the spherical. These ordered composites will contain unique network structures and arrays of interpenetrating phases to meet the structural requirements of "smart composites" with proper connectivity patterns. hexagonal.. Braun.be synthesized. 1993. Figure 16.. it is conceivable to prepare other highly ordered nanocomposites based on these ordered liquid crystalline structures. 235 .10 illustrates several important template structures formed by the surfactants. 1995.

Ia3d). This produced mesoporous materials with thick walls and small grain sizes.. in which the surfactants and the ceramics are similarly charged and bind together through an intermediate ionic species of opposite charge (Huo..3. 1995). have been observed (Huo. Neutral surfactants can be also used (Tanev and Pinnavaia.1. Apparently. mesoporous silicates can be synthesized under a variety of experimental conditions. hexagonal (P63/mmc.3 Binding with Surfactants The preparation of ordered mesoporous materials can be also classified based on what surfactants are used and how they are bonded to the ceramic phases. 1994). including several lamellar. The initial Mobil (MCM-41 series) silicate-based materials were prepared using direct ionic bonding with a cationic surfactant. The neutral synthesis route used uncharged (dodecyl amine) or nonionic surfactant (polyethylene oxide). et al.. The surfactant can be removed by simple solvent extraction. 1995). et al. P6m). and cubic phases (Pm3n. A more generalized synthesis route was developed to include ion-mediated ionic bonding. 1995. The oxide precursor was bonded to the surfactant through hydrogen bonding. A range of ordered phases.16. A ligand-assisted templated approach using amine surfactant was also developed 236 . et al. Bagshaw.

and acidity (Sayari.3. et al. However. sensing controlled release. etc. high-quality. In this approach the ceramics (alkoxide) is covalently bonded to the long-chain amine surfactant before the hydrolysis and condensation of the precursor. 16... The terminal functional groups on the monolayer can be easily modified. 1994). 1997. ion exchange. This allows the selective hydrolysis and condensation of the oxide precursor on the micellar surface and prevents the uncontrolled precipitation of particulate oxide materials that is commonly observed in non-silicate materials. stereochemical configuration or charge density.. Schierbaum. Liu. et at. size.2 Hybrid Nanoscale Materials Many applications have been considered for the new mesoporous materials. et al. Table 16. 1993.1 Different approaches according to the surfactant and the interfacial bonding Surfactant Cationic A+ Bonding Direct ionic Mediated ionic Anionic ADirect ionic Mediated ionic Neutral A0 or nonionic Hydrogen Neutral amine Amphoteric A+B Mediating ions None Anionic XNone Cationic X+ None None None Inorganics Anionic MCationic M+ Cationic M+ Anionic MNeutral M0 M(OEt)x Aqueous precursor M Conformation A+MA+X-M+ A-M+ A-X+MA0M0 –H2N–M(OEt)x A+B–M Covalent Covalent 16. adsorption. The functional molecules are closely packed and cross-linked with one another. 1998).1. 1996. et al. In this approach. Most mesoporous materials do not themselves have the appropriate surface properties. transition metals. including energy storage. thereby allowing rational design and layer-by-layer construction of host sites on the nanoporous substrates that match the shape.12) (Feng.2.1 Molecular Monolayers in Ordered Nanoscale Materials A method has been developed to systematically modify the surface chemistry and tailor the molecular recognition process of mesoporous materials toward the targets (Fig. or chemical properties of heavy metals. 16. The various chemical binding conformations involved with surfactants are illustrated in Table 16. most of the applications require the materials to have specific binding sites.to prepare transition metal mesoporous materials (niobium and tantalum oxides).3. catalysis. 237 . oriented molecular monolayers are spontaneously grown on ordered mesoporous ceramic substrates with controlled pore shape and pore size. Anthony..

making them extremely efficient scavengers of these species. Figure 16.2 Application for Specific Adsorption One application we studied involves alkyl thiols [tris(methoxy) mercaptopropylsilane.. with permission from Wiley-VCH). 1986).2. Figure 16. neutral and basic solvents). oil.or organic molecules. We selected TMMPS because it has been previously used to make functional monolayers. 238 . divided by metal concentration (µg/mL) remaining in the treated waste stream. or effective catalysts for reactions involving these species. A single treatment of highly contaminated water usually reduced the mercury concentration to well below U. Industrial and civilian sources deposit a large amount of mercury into the environment every year (Mitra.S. The thiol-silica hybrid mesoporous materials thus produced can efficiently remove mercury and other heavy metals (such as lead and silver) from contaminated aqueous and organic solutions. has been measured as high as 108. As such. et al.3. Mercury and heavy-metal contamination is a serious problem at waste contaminated sites of the Department of Energy (Klein. 1998. acidic.13 shows the mercury concentration remaining in the waste solution as a function of treatment time.12 Formation of molecular monolayers in ordered mesoporous supports (Liu. A loading capacity of 600 mg (Hg)/g (absorbing materials) has been obtained. The distribution coefficient. 1994). 16. TMMPS] as the functional molecules for heavy metal remediation.) The exceptional selectivity and capability of hybrid materials to remove mercury and other heavy metals from contaminated solutions have been demonstrated under a wide range of conditions (water. Kd. and the thiol groups have a high affinity for binding heavy metals. The hybrid materials remove the Hg in the water much faster and to a much lower concentration. Environmental Protection Agency elemental limits for hazardous wastes and even drinking water standards. (Kd is defined as the amount of adsorbed metal (µg) on 1 g of adsorbing material.

such as methylmercury. which are major concerns in drinking water. The mercury-loaded materials were heated in water at 70°C and released little mercury. (Liu.Similar results have also been obtained for lead and silver. zinc. Methylmercury exists in the environment through methylation of mercury by methanogenic bacteria that are widely distributed in the sediments of ponds and in the sludge of sewage beds. Figure 16. one of the most toxic forms of mercury.. In addition. sodium. The mercury-loaded materials can be regenerated by washing in a concentrated HCl (12. et al. In situ NMR experiments indicated the bonding between the mercury and thiol group and the structure of the organic monolayers are stable up to 125°C. with permission from Wiley-VCH) 239 . Similar loading capacities have been obtained for mercury ions (Hg2+ in mercury nitrate) and methylmercury. The performance of the materials is not affected by the presence of background electrolytes (ions of barium. 1998. the hybrid materials have other advantages. and the comparison with commercial materials. A very small amount of methylmercury can be fatal to the human body. such as stability and recyclability.13 Hg concentration remaining in the solution as a function of time when the functionalized mesoporous silica was used as the sorbent. The hybrid materials have also shown high efficiency in treating different species. or nitrate).1 mol/L) solution.

are included in the U. 1976). is shown in Fig.Another application is arsenate removal (Fryxell. The adsorption isotherms for removing arsenate and chromate from contaminated water are plotted in Fig. Nearly complete removal of arsenate and chromate has been achieved in the presence of competing anions for solutions containing up to 100 ppm toxic metal anions under a variety of experimental conditions. unlike many heavy metals and transition metals.. Figure 16. (Fryxell. 1983..15. 16. The mesoporous silica was functionalized with an ethylenediamine (EDA) terminated silane [(2 aminoethyl)-3-aminopropyl trimethyl silane]. We synthesized and used metal chelated ligands immobilized on mesoporous silica as an efficient anion binding material for both arsenate and chromate. These contaminating species. along with other toxic metals like chromium and selenium.14 Cage structures of EDA-Cu complex generated by computer modeling. generated from computer modeling using the PM3 and PM3™ Hamiltonians (Stewart and stewart. Currently. 1996. Environmental Protection Agency's list of priority pollutants. when the stoichiometry of binding and the atomic/molecular weight of the target species are taken into consideration. can exist in nature as tetrahedral oxyanions (arsenate ions HAsO2-4. Good selectivity between chromate (or arsenate) and sulfate ions can be achieved at high anion concentrations. et al. Recent reports of the crisis caused by arsenic contamination of drinking water in Bangladesh and other parts of the world have attracted wide public attention (Nickson. H2AsO1-4. 1998. metal loading capacity achieved with the best cation sorbent materials (functionalized mesoporous silica) discussed earlier.S.. and chromate ions HCrO-4. 1994). et al. In Bangladesh alone. et al. The anion loading capacity of this material is comparable (on a molar basis) to the heavy. Inc. forming an approximately octahedral Cu(EDA)3 complex structure. et al. trace amounts of arsenate and chromate need to be removed from waste solutions containing high concentrations of competing anions. This approach is especially promising considering the rich chemistry that can be explored with monolayers (Whitesides. 1996). The C3 symmetry is ideal for tetrahedral anions. the development of effective anion binding materials is an important subject in chemistry. health officials estimated 50 to 70 million people could be affected by drinking water contaminated by natural arsenic sources. 1999). 1999. http.. Irvine. 1995.. Von Carman Ave. 1989 and 1990). with mesoporous silica. CA). biochemistry and materials and environmental science (Woolson. with permission from ACS) 240 . Cu(II) ions were binded to the EDA monolayer with a 3 to 1 EDA to Cu ratio. 1999). Ulman. as implemented in PCSpartan 5. sulfate. Anion loading is more than 120 mg (anion)/g of adsorption materials.1 (Wavefunction.. CrO2-4) (Baes and Mesmer. In many cases. Atwood. 16. and chloride in particular. Arsenic. et al.14. The cationic octahedral complex contains an electrophilic basket with C3 symmetry that forms an ideal host for a tetrahedral anion. This complex structure. Schierbaum. Most of the anion treatment technologies are not very effective. and the possibility of designing better anion recognition ligands.

Figure 16.. et al. with permission from ACS) 241 . 1999.15 Adsorption isotherms of chromate and arsenate using EDA-Cu modified mesoporous materials as the sorbents. (Fryxell.

. it is difficult to disperse and stabilize TPA on high surface area mesoporous silica. 16. (a) Phase segregated Cs-TPA. Soled. 1992. Figure 16.17(a)) gave much higher conversions. HF and H2SO4 liquids are used as homogeneous catalysts for the commercial alkylation process (Misono and Okuhara. The high surface area and the uniform pore channels make the mesoporous materials ideal catalyst supports. 16. One solution to this problem is to replace the liquid acids with solid acid catalysts. The proton in TPA can be partially substituted with Cs+ to form Cs-TPA. 1995. as shown in Fig.3 Application for Catalysis Finally. which produced a more homogeneous catalyst material.. TPA) (Misono and Norjiri.17. However.16(b). one area of great importance is found in using mesoporous materials as catalysts or catalyst supports. Okuhara. 1999). We will use the preparation of solid-acid catalyst as an example (Choi. et al. et al. Traditionally.. 1993). 1990. 1993.16(a) shows that simple impregnation technique just produced a material in which the Cs-TPA catalyst was phase segregated from the mesoporous support. the uniformly dispersed catalyst (Fig. The catalytic activity was evaluated using alkylation of trimethylbenzene (mesitylene) by cyclohexene as a model reaction. therefore defeating the purpose of using a high surface area support. 1999). 16. The TEM image in Fig.. The corrosive and toxic nature of such chemicals presents a problem for the environment and for the operation. Clearly. 1996). Corma. et al. such as tungstophosphoric acid (H3PW12O40. 242 . The key is the dispersion and stabilization of the catalyst on the support. Corma and Matinez.16(b) are plotted in Fig. The catalytic properties of the two materials corresponding to Fig. which improves the thermal stability (Okuhara. 16.3.2.. We also used a modified grafting technique.16 TEM images of Cs-TPA dispersed on mesoporous silica. 1997). which is a stronger acid than 100% H2SO4. et al.16.16(a) and 16. et al. The conversion percentage is plotted as a function of Cs stoichiometry. (b) Dispersed Cs-TPA (Choi. 16.

G. 34. and C.. E. J.. Ying. 503.. G. W. K. 865 (1995) 243 . C. (1993) Antonelli D. 13. et al. 16. J. and R. C.17 Conversions of tremethylbenzene by cyclohexene as a function of Cs stoichiometry. Y. Commun. 366 (1995) Atwood J. 1401 (1996) Baes C. The Hydrolysis of Cations.. Engl... and with the increased ability to take advantage of more complicated organized structures and processes. Steed. V. Ed. Dosch. L. A. will arrive with a better understanding of the role of the directing molecules. 2014. Nature. Philips. Pinnavia. Holman. M. 1995 (1995) Attard G.4 Summary and Prospects Molecularly directed synthesis of nanophase materials and nanocomposites have shown great promise as a new approach to prepare a wide range of organized nanoscale structures and functional materials. E. and T. Int. Glyde. A. Prouzet. F. Chem.. Angew. J. (2) Phase segregated catalyst (Choi. Novel materials. Waste Management. References Anthony R. and more sophisticated functional nanocomposites. and J. G. John Wiley & Sons: New York. Goltner. 378.Figure 16. (1) Dispersed catalyst. 267. Mesmer. Jr. (1976) 215 and 366–368 Bagshaw S. Chem. novel applications. 1999). R. T. Science.

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. (b) teeth. Nacre has a fracture toughness of about three orders of magnitude higher than that of monolithic aragonite (a type of CaCO3). is the notion of hierarchical structure. biological systems have been the inspiration.. 1999). with (a) abalone. 1998. Wang. Recent studies of biological ceramic composites (bone and teeth. 1997.) have generated a number of new ideas on how structure can affect material properties (Weiner and wagner. etc. Detailed studies of the structure of nacre have provided clues for materials scientists hoping to mimic nacre's microstructure in fracture-resistant synthetic materials.17. 1998. Simply stated. mollusk shells. 1990. 1998. The nacreous layer of mollusk shells is one example of this phenomenon. 1993. Weiner and Addadi. 1988. and (c) radiolaria.1 Examples of biological structures that have inspired new materials. Wang. Smith. Aksay and Weiner. et al. hierarchical structure refers to the existence of structural organization at multiple length scales (often nanometer to micrometer.. The mortar is made out of polysaccharide and protein fiber saligned orthogonal to each 246 . all materials possess some degree of organized structure at multiple length scales. 17. In the case of biological ceramic composites. Figure 17. to millimeter) within a given material.1. Of course. organic phase controls the structure of the mineral phase at multiple length scales in a manner that leads to dramatic improvements in the mechanical toughness over bulk mineral. Mollusk shells are mostly CaCO3 and about 5 wt% protein. Nacre owes its fracture strength and toughness to its composite organic/inorganic microstructure. et al.1 Introduction This chapter examines a relatively new paradigm for tailoring the mechanical properties of composite materials. 1997. As has often happened throughout history. The most important idea to emerge. A fractured abalone shell exposes a brick and mortar arrangement. Examples of such structures are shown in Fig. et al. Nanostructured Bio-inspired Materials 17. the key is that this organization occurs in such a way as to cooperatively enhance a given property. and the focus of much of this chapter. Berman.

A mortar layer. which are ordered at the nanometer level.e. 17. can be seen within the mineral tablets. (c) High-resolution TEM mage of interface between brick and mortar phases. which results from the well-ordered composite nature of mineral and the collagen matrix. bone. 17. The bricks of highly uniform aragonite (thickness 0. which separate the aragonite lamellae (Fig. and mineralized turkey tendon) are constructed from the same building blocks. the mineralized collagen fibril. This templating effect occurs at both molecular length scales (where the protein serves as a nucleation site) and higher (the nucleation sites are arranged in a larger framework which imposes organization at larger length scales). (b) Cross-sectional TEM image of nacre. The cross-sectional transmission electron image (TEM) reveals organic mortar layers. continuous with the interlamella sheets separates laterally adjacent tablets.2(b)). The variation in mechanical properties is due to differences in the way the collagen fibrils are assembled—in short. and the organic phase is composed of a mixture of protein fibers and nano-aragonite inclusions (Fig.5 µm) in interdigitated columns (Fig. One of these is the idea of templating. roughly round in cross section.2 (a) SEM image of abalone nacre exhibiting interdigitated stacks of aragonite tablets. a few general principles are commonly accepted. the organic phase (typically proteins) serves to direct the structure of (template) the mineral phase. Typical interfaces between two phases are not atomically smooth.. Furthermore. In biological ceramic composites. Efforts to develop and manipulate artificial systems with 247 . due to the various hierarchical structures (Weiner and Wagner. The curved lateral boundary between coplanar tablets can also be seen. The development of hierarchical structure is still an area of active research. approximately 10 nm thick. Although members of this family of materials (i. These materials share one common feature. Although many of the details are still unclear. This mechanism may be responsible for the nucleation and growth of the crystal. Figure 17.2(c)). cementum. the aragonite phase is composed of regular single crystalline CaCO3 structure.2(a)). organic inclusions. These observations hint at some mechanism for the sequestering of soluble organic material within the aragonitic crystals. 1998). high toughness. dentin. they have mechanical properties suited to their specific functions.other and parallel to the aragonite crystal axes. 17. The mineralized collagen tissue is another natural example of improved properties due to hierarchical structure.

Methods for simultaneously controlling the structure from atomic to macroscopic length scales still need refinement. In addition to chemical control.. Firouzi. et al. cooperative structural control at multiple length scales is desirable. First. Early in the growth. mesoscopic silica)(Trau.g. Although our understanding of how to specifically structure a material is still embryonic. we will discuss recent efforts for applying some of the insights gained. the organic phase can also affect the mineral structure by forming a physical framework. 1997). These hierarchically structured composites are formed using some of the principles described above. A good example of this effect is collagen in bone.hierarchical order have shown that applied fields further impose or augment structural control at multiple length scales in organic-inorganic systems (e. The oriented growth of Ca-P minerals within a collagen framework has also been successfully demonstrated by in vitro experiments (Wang and Weiner. Dentin fulfills a vital function in many vertebrates. Type I collagen forms a 3-D ordered framework for mineral formation. while macromolecules extracted from the calcitic layer of the same shell only induced calcite formation. There is a high degree of specificity in the nucleation and inhibition processes. specifically dentin.. 17. et al. these macromolecules control the nucleation and orientation of a specific mineral. Hillhouse. In later stages.. et al. 1999). there is no question that the structure of successful synthetic analogues of biological composites will need to be closely controlled. we take a closer look at a naturally occurring material—–teeth. 1997. They can serve to initiate or halt the growth of the crystalline mineral phase. The remainder of this chapter is devoted to case studies of two hierarchically structured materials grown through a templating process. In the second case study. we will examine the concepts of hierarchical structure and the role of organic species in templating in the context of dentin. Special attention is paid to the hierarchical structure and its resulting improvements in mechanical properties. the idea of templating through a ternary phase (usually organic) is a flexible and effective way to manipulate structure of materials at multiple length scales. the fact that we are able to apply some of the principles of hierarchical ordering in an artificial system is a promising step in the right direction. Inside each collagen fibril. The insights gained from the study of natural systems point to two general principles for the design of synthetic high-performance composite materials. Although we are not yet at a point where we can tailor the mechanical properties of these materials. the texture and organization of crystals are controlled by the organic phase. 1997.2 Case Study I: Teeth In this case study. as well as 248 . Growth is terminated by the selective adsorption of macromolecules onto crystal surfaces or by impingement of the crystal on a preformed organic framework (Weiner and Addadi. We will also illustrate how the ideas of templating and directed growth emerged from studies of tooth growth and structure. It was found that acidic macromolecules extracted from the nacre were capable of inducing aragonite crystallization. 1998). Biological macromolecules (usually acidic) play a key role in the templating process. In the first case study. Second. One synthetic system that has and continues to receive much attention is mesoporous silica films. mineral growth is guided by aligned grooves between many triple helical molecules.

1994. while absorbing part of the working energy.3 Labio-lingual section of a human incisor. 1990). Studies on dentin have revealed that its mechanical toughness results from two features: precise control over mineralization at the nanometer scale and the presence of cooperative hierarchical structures. This is an indicator of the mechanical function of dentin. 17. They are composed of a very dense outer enamel layer.2.invertebrates. readers are encouraged to read recent articles and reviews (Weiner and Wagner. microcracks are always found on the enamel surface of adult human teeth. It effectively transfers stress from the outer enamel layer into the jawbone. yet very tough. but they usually do not penetrate into dentin. with the notable exception of fish. Studies of the structure of teeth and its relationship to mechanical performance at various length scales provide invaluable opportunities to relate function to structure. Figure 17. Most vertebrate teeth. Its structure is presumably fine-tuned to specific mechanical requirements—the cutting. Aksay and Weiner.1 Control over Mineralization at Nanometer Scale 249 . Clinically. 17. crushing and grinding of food. it is designed for cutting and grinding food. Weiner and Addadi. 1997. The supporting dentin is relatively soft. Enamel is hard but brittle. For detailed information on other biological materials. which is present only on the working surface. have the same basic structural pattern. 1998). and a less dense but generally thicker inner layer of dentin (Fig.3) (Ten Cate. 1998. Carlson.

crystals of mineralized collagen fibrils are aligned with the crystallographic c-axis parallel to the collagen fibril axis and the plate surfaces are parallel to each other (Figs. The hexagonal axis is always perpendicular to the plate surface. (c) Models showing the proposed location of the platy crystals in the channels.. 1962). with average lengths and widths of 50 nm×25 nm and a thickness of 1. 20 wt% organic materials. Hohansen.5) Figure 17. 1998. including the various types of bone. Lowenstam. et al. 1989).. and 10 wt% water (Wang. 1989) Figure 17. 17.5–4 nm (Weiner and Wagner. 1989). (b) 3-D model showing the alignment of the holes to form a channel (Yamauch.. et al. These fibrils contain about 70 wt% carbonate apatite minerals (Ca5(PO4. et al.4). et al.2 µm). and the c-axis is parallel to the long axis of the plate. et al.. 1998). Collagen (Type I) is one of the main components of the three-dimensional matrix into (or onto) which the mineral crystal forms an ordered structure (Fig. et al. (Traub. 250 . 1989.Dentin is a member of a family of materials. Furthermore. (a) Collagen molecules (represented by rods) aggregate into a quarter-staggered pattern described by Hodge and Petruska.4 and 17.5 A twisted mineralized turkey tendon fibril in vitrous ice showing the apatite mineral plates both edge-on (B) and face-on (A). These materials all have the same structural building block—the mineralized collagen fibril (Weiner.. (1963). CO3)3(OH))... 1998). (Veis. et al. The apatite crystals in mineralized collagen fibrils are plate-shaped. 17.4 3-D organization of apatite minerals inside collagen fibrils at nanometer scale. (Bar = 0.

In mineralized turkey leg tendon.4 directly results in the anisotropic mechanical properties at higher levels of structure. The basic mechanisms underlying the genetic control over crystal precipitation are the main focus of biomineralization (Lowenstam.. The above evidence strongly suggests that both the nucleation and growth of the minerals have been well controlled in this biological system. and is lowest on the plane parallel to the collagen fibrils where the plates are face-on (Ziv. et al. et al. where the crystal plates are oriented edge-on.. 17.Many non-collageneous proteins (less than 10% of the total proteins) exist between the collagen and crystals as well. 1989). et al. microhardness is highest on the plane perpendicular to the collagen fibril axis. 251 . The orthotropic structure of mineralized collagen fibrils shown in Fig. and that the enhanced mechanical properties originate at the nanometer level where the minerals are organized within the matrix frame. a research field now closely linking biology to materials science. the elastic modulus is the highest in the direction parallel to the collagen fibril axis and is the lowest in the orthogonal direction (Lees.. 1996). 1992). In parallel-fibered bone.

often crosslinked. and at the same time it gives rise to anisotropy.. biological materials have distinct levels of organization. which are composed of two α1 polypeptide chains and one α2 chain.2. High levels of structure (larger length scales) provide properties that make each member within a family unique. Inside each collagen fibril. Both types of macromolecules are present at the nanometer level. Those two levels are common in dentin.5 nm). The first two levels (the molecular components and the collagen fibril) have been described above. within which the fibrils are aligned to each other only with their fibril axes. Low levels of structure (smaller length scales) determine the fundamental properties. The collagen fibrils in dentin form small bundles. They mediate mineral growth in different ways. type I collagen forms a three-dimensional ordered framework for mineral formation. The corresponding features in dentin are described here. 1998). et al. They are more hydrophobic. which is overcome at higher levels of organization. 17. et al. 1989. In dentin and other mineralized collagen tissues. The collagen fibrils are a clear example of the composite nature of bone family (Fig. carboxylate groups. 17. 37 nm high in the direction of the fibril axis. mainly through illustrating the structure of bone (Weiner.. phosphate or sulfate groups) and closely interact with the mineral ions in solution or with the surfaces of the solid phase.2 Hierarchical Structure in Biological Materials In much the same way a building is organized at the multiple length scales of bricks. and relatively insoluble. walls.5). These aligned grooves provide the nucleation sites (with the presence of acidic noncollagenous proteins) of minerals and guide the growth of plate-shaped minerals (Fig. The main function of these macromolecules is to provide a three-dimensional matrix from which the control proteins interact with the mineral phase (Weiner. 17. 1992). Wang. rooms and finally the whole structure.4 (c)). bone and the mineralized tendon. et al. Numerous in vitro studies have indicated that mineralization and control over crystal growth are accomplished through these molecules.g. 1997).4 (a)). The resulting structure has transversal isotropy. The "framework macromolecules" constitute the bulk of the organic matrix in biological materials.. "control macromolecules" and "framework macromolecules". 1997). Control macromolecules usually contain charged groups (e. are arranged in a staggered array. The oriented growth of Ca-P minerals within collagen framework has also been successfully demonstrated by in vitro experiments (Iijima. These macromolecules can be divided into two main groups (Weiner. 252 . Phosphorated proteins are control macromolecules in the dentin of teeth (Veis. 1989). which distinguish one family of materials from another. 1998). Addadi. et al. These holes are aligned to form transversely contiguous grooves. A gap (or hole) exists between the NH2-terminus of one triple helical molecule and the COOH-terminus of the next (Fig... 1998). many triple helical molecules. cementum. 1997.. which are one molecule thick ( 1.4 (b)). They contribute to the well-known toughness of bone-like materials. typically through electrostatic interactions (Veis.A number of biomineralization studies have found that biological macro-molecules are the key to controlling mineralization. 17. Each mineralized collagen fibril is rotated around this axis in such a way that the mineral plates from adjacent fibrils often have different azimuthal orientation (Wang. 17. et al. Bundles of collagen fibrils comprise the third level of structure.. Weiner and Wagner have described seven hierarchical levels of organization in the bone family. et al. and extend for some unknown distance across the fibril (Fig.

It is these two levels of organization that differentiate dentin from bone and other mineralized collagen tissues.. in the planes parallel to the surface at which dentin formation takes place (Fig.6 (b)). which is closely related to elasticity (Wang. 1998).6 Ultrastructure of (a) cow root dentin and (b) coronal dentin. 1998). the random orientation within layers and the transversal isotropy of the bundles produce isotropy in Vickers microhardness. 17. This "design" of mineral gradient could protect the dentin-enamel junction from failure and facilitate the even transfer of stress from enamel to dentin. Within these incremental planes. At the sixth level of organization the difference between two types of dentin (root dentin and coronal dentin) can be seen. 17. Figure 17. Dentin immediately underneath enamel has much lower mineral content and is softer than the central part of the dentin (Fig.. 17. 253 .. 1998). The layered structure results in much higher cracking resistance in the direction perpendicular to the incremental planes than parallel to them (Wang. highly mineralized peritubular dentin forms a cylinder surrounding each dentinal tubule in the coronal dentin (Fig. At the fifth level. the fibril bundles are either randomly distributed (coronal dentin) or poorly oriented (root dentin) (Wang. et al. surrounding dentinal tubules. A dense.The collagen bundles at the "fourth" level of organization are laid down. the relative content of the mineral and the density of the dentinal tubules are systematically changed from central pulp cavity side of a tooth to the peripheral sides.7). At the same time.6 (a)). et al. As a result. et al.

the mesoporous silicates. 17. 1992). (Wang and Weiner. molars. They prepared this structure using an inorganic/organic templating mechanism. A recent class of materials. premolars. incisors.coronal dentin has higher elastic modulus than root dentin.3 Case Study II: Mesoscopic Silica Films In this case study. and the size and geometry of a whole tooth construct the highest level of the hierarchical structure (Fig. where silica condenses around a surfactant micelle mesophase (Fig. It is also more isotropic in fracture properties than root dentin. 254 . etc. researchers at Mobil Research reported the successful synthesis of silica molecular sieves.. with variable.3). In 1992. Figure 17. et al.8). designated M41S. and the lower gray side is dentin.7 Backscattering scanning electron image of a section from a human premolar. their relative thickness. 1998) The combination of dentin and enamel. The upper white part is enamel. canines..5 nm to 10 nm) and morphologies (hexagonal. The dark zone next to enamel showing lower mineral content in that dentin area. pore sizes (1. but monodisperse. we will describe one way in which some of the concepts from biological composites have been used in the design of synthetic materials. 1998). 17. et al. as shown by indentation studies (Wang. cubic and lamella) (Kresge..) and teeth of different species come to function. will be examined.e. This is the level where different types of teeth (i. in which amphiphilic molecules are used to control the growth and structure of an inorganic matrix. 17.

Researchers at Princeton. we will describe the hierarchical structure observed in 255 . et al. et al. Several comprehensive reviews have been published describing these recent directions and results (Maschmeyer. et al. Subsequent studies have shown that pore size and packing can be adjusted by varying the surfactant or introducing additional species in the reacting solution and that the pore morphology of the silicate product is closely linked to the structure of the surfactant mesophase (Vartuli. and other forms of mesoporous silica. Mesoporous silica is currently an extremely active area of research.. et al. could be used as the structure determining agents (Zhao. (b) morphologies: cubic. 1998b).. et al. Researchers at the University of California at Santa Barbara demonstrated that the synthesis of mesoscopic ceramics could be generalized by categorizing them according to the electrostatic interactions between the organic and inorganic molecules (Huo.. where the inorganic infiltrates and solidifies a pre-existing ordered amphiphile array. 1997). et al. 1998. Sandia National Laboratory. 1997. 1996. silica. the concentrations of amphiphiles are too low to produce the observed channel packing. Ozin. gold overlain with patterned organic thin films and the air-water interface (Ryoo. Fibers. et al.. et al. 1999. UCSB and Toronto were among the first to report thin films. as well as amphiphilic block copolymers. et al. lamellar.. they showed that neutral surfactant species (Attard. 1998a). the UCSB group concluded that the inorganic species plays a non-trivial role in determining the final structure.. 1997. "Co-assembly" is the term applied to this situation to distinguish it from direct templating. Later. Trau.. 1994). et al. gyroids and other shapes have resulted from modifications of the solution composition (Lin. tubes.Figure 17. et al. fibers. A number of research groups have shown that other macroscopic morphologies are possible. Yang. 1994. hexagonal. others have opted to move toward commercial applications by derivatizing the molecular sieves. Some research groups have concentrated their efforts on understanding and extending the templating process. In the remainder of this section. et al. 1996. mica. et al. The first mesoporous materials prepared were micron-sized particles. spheres.. 1997).. Yang. 1994. Yang. Thin films have been grown using direct templating and dip-coating methods (Aksay... (c) pore size control by inserting organic spacer molecules. 1995).. Thus. Lu. 1996. on materials. Zhao. such as graphite. 1996). Beck. et al. 1997).. Under most synthesis conditions..8 Organic-inorganic templating: (a) schematic of templating.

. For example. Indeed. The use of amphiphilic block copolymers allows materials with even larger pores to be made.3. That is. or TEOS). 1994. however. Both XRD and TEM analysis show that mesoscopic materials have channels that are packed along a hexagonal lattice with an average channel spacing of about 4 nm. et al. There is also interest in controlling the long-range orientation of the channels. et al... The purpose of this section is to document the hierarchical order present in this entirely synthetic system. et al. Although the manner in which structure is controlled may not be as elegant as protein-directed dentin growth. still allows for the meandering of channels along their axes. hexagonally packed channels are spaced according to a regular lattice. Films appeared at the air-water interface. an entire bundle of channels may bend in unison. the surfactant system responds in the same way as a liquid crystal. Aksay. et al..1 Nanometer Level Structure At the nanometer level. it has been found that the addition of cosolvents can cause a system of hexagonally packed channels to adopt a cubic or lamellar configuration. Huo. along the sides of the container and on any substrates included in the container. 17. or CTAC) and an alkoxysilane precursor (tetraethylorthosilicate. increasing the organic tail of the surfactant leads to larger pore diameters.1 Hierarchical Film Structure The biological principle of organic-directed mineral growth is operative. 1997). et al.mesoscopic silica thin films grown in our lab under acidic conditions and illustrate how to achieve hierarchical structural control. The channel organization can be manipulated using similar guiding principles.1. in the growth of mesoscopic silica thin films. et al. Films grown on solid surfaces are described at length elsewhere (Aksay. 1994. if no surfactant is added to the system. the resulting material lacks channels. 256 . In some cases.3. Yang. 17. 1996. the development of a rigorous method of predicting channel organization based on the initial composition of the system is still being actively pursued.. This suggests that the surfactant plays a critical role in initiating film growth as well as directing mesoscopic structure. The films described in this section were grown at room temperature under quiescent conditions in a dilute acidic (pH<2) solution containing surfactant (cetyltrimethylammonium chloride. maintaining regular packing while at the same time having poor long-range order. albeit in a simplified manner. 1996). The exact mechanism by which the surfactant affects structure at lengths larger than the channels is not completely understood. silica thin films formed in this manner possess regularly packed channels. however. For example. Qualitatively. Zhao. the success in applying the biologically inspired principle of organically directed mineralization is an encouraging result. Channel size and organization can be controlled in a number of ways (Vartuli. 1996. The same effect can be accomplished by introducing ternary organic components which "swell" the micelles. As might be expected. The channel diameter corresponds to the approximate diameter of a surfactant micelle. the packing organization dictates the local orientation. 1997.. This.

(a) and (b) illustrate the periodic mica and graphite atomic lattice onto which CTAC adsorb and orient. compressed in the direction normal to the template.9 (a) reveals a slight elliptical distortion of the tubules suggesting that the films are strained.10 TEM image of a planar cross section of a film grown on silica. This section was taken through a macroscopic swirl similar to those shown in Fig.9. These values suggest that the film is not highly distorted.10 shows a TEM planar cross section of a film grown on silica. Typical TEM images of a mesostructured silica film grown on mica are shown in Fig. Figure 17. and amorphous silica substrates. Inset: SAED patterns indicating regular hexagonal packing and parallel channels. Images of the films 257 .12 (c). 17. 17. Figure 17. e. In contrast to those shown in Fig. this image exhibits a spiraling and twisting arrangement of surfactant tubules. respectively. Figure 17. Side view (a) and head-on (b) images are shown. The channels in Fig. Figure 17..9. i. Figure 17. graphite. graphite.One interesting way to influence the long-range channel orientation is by introducing an interface. AFM images of the mica. amorphous silica substrate.9 Cross-sectional TEM images of the final film interior.11 In situ AFM images of mesostructured films growing on mica. perpendicular to the film surface. and (c) reveals a smooth.7 (a) show a -5% to 10% strain in both the parallel and perpendicular directions. 17. 17. Both images are in a transverse orientation with respect to the film and reveal hexagonal packing of tubules aligned parallel to the substrate. and silica substrates used to grow mesoscopic silica films are shown in the insets.

oriented parallel to the solid/liquid interface. Tubules are initially aligned along one of the three next-nearest-neighbor directions of the mica oxygen lattice displayed in inset. along one of three symmetry axes of the hexagonal carbon lattice shown in inset. Manne and Gaub. these do not meander. periodic dimples are observed rather than stripes. 1994). (c) On amorphous silica.. 1994. tubules align parallel to the substrate.were obtained in "non-contact" mode. In the early stages of the reaction (<7 h). however.8 nm spacing.. 258 . 6.2–6. et al. On graphite. Senden. suggesting an orientation of the tubules away from the interface. et al. (a) reveals meandering surfactant tubules on the mica substrate. Unlike the mica case. form rigid parallel stripes. 1995. utilizing the electrical double layer force described (Manne. this orientation is preserved as tubules continue to assemble and grow away from the interface coupled with silica polymerization.

respectively. Oriented tapes are observed on mica and graphite. (c) silica/water interface for 24 h.Figure 17. (b) graphite/water. 259 . The films grown at the silica/water interface are uniform initially (dark background) but spiral like structures (light features) form later.12 SEM images of mesoscopic silica films grown at (a) mica/water.

et al. Although the molecular organization and self-assembly of surfactants at 260 .This behavior can be explained by considering the structure of the micelle layer that is adsorbed at each interface (Aksay. 1996)..

acidic (pH<2) conditions. Yao et al.1. parallel stripes without the meandering curvature observed on mica. 1995). the micron structure may be the result of the grains. Films grown on mica (Fig. More recently. graphite and silica interfaces are shown in Fig. 17. 2000).12 (c)) exhibit dramatically different orientations. 17. The first step is the self-assembly of surfactant at the interface to form meandering tubules. Adsorbed hemi-micellar arrangements are observed on poorly orienting amorphous substrates. It is remarkable that features at the length scale of atomic dimensions (mica and graphite lattice) can influence the structure at nanometer and micron length scales in such a pronounced manner..12. 1996). Micelles adsorbed onto mica and graphite surfaces appear to recognize the asymmetry in the underlying mica lattice. Aksay et al. The weakly interacting silica surface may be insufficient to impose long-range orientational order on the micelle assemblies. 17. Surfactant tubules appear to register the underlying lattice of the substrate. This argument is further supported by an elegant investigation at the early stage of film growth.12(a)) and graphite (Fig.. The role of organic species in directing the structure at the micron level is more subtle when compared with the nanometer level. et al. et al. The latter substrates orient adsorbed surfactants via anisotropic attraction (either van der Waals or electrostatic) between the crystalline substrate and the surfactant molecule.12 (a)) owing to its distorted hexagonal structure. The amorphous silica substrate has no preferential orientation for surfactant adsorption. such as silica. Recent work has shown that 3-D surfactant structures such as cylindrical tubules and spheres can form at solid/liquid interfaces (Manne.12(b)) exhibit preferred orientations at mesoscopic and in-plane confinement at microscopic length scales.interfaces is a widely studied area. By contrast. et al. but over time develop 3-D structures. Figure 17. et al. 17. 261 . Two directions are preferred for surfactant micelles adsorbed on mica (Fig. most notably particle-like bundles. reported a detailed study of the mesoscopic (nanometer level) and microscopic (micron-level) structural evolution of mesoscopic silica thin films grown at the air-water interface under dilute. Micelles at silica interfaces (Fig. 17. SEM images of the films grown on mica. films grown on silica surfaces are initially uniform.. Further. This work clarified the role of the air-water interface in confining film growth to two dimensions during the initial stages and provided a detailed mechanism for the development of mesoscopic order and microscopic features and considered the possibility of a universal growth mechanism for films and particles (Yao. As polymerization continues. Silicon hydroxide monomers (or multimers) polymerize at the micellar surface. 1994). films grown on mica and graphite seem to possess the same orientation constraints.2 Micrometer-Level Structure The principle of hierarchical order directed by organic species also manifests in the mesoscopic silica system. While the nanometer structure is likely the result of individual micelles. 17. and aligned tubular structures are observed on more strongly orienting crystalline substrates such as mica and graphite..12 (b)) the surfactant tubules are also aligned parallel to the surface. in this case they are rigid. 17. little is known about the precise structure of adsorbed surfactant layers.11 shows in situ atomic force microscopy (AFM) images of the atomic lattice of each substrate as well as the structure of the mesoscopic silica overlayer growing on each surface (Senden. however. On graphite substrates (Fig. more surfactant is adsorbed to the freshly formed inorganic surface allowing the templated mesoscopic structure to replicate itself and grow into the bulk solution.3. showed that there is a sequential process of film growth (Aksay.

The ability to impose arbitrary micron sized features may also be important in the development of commercial applications for mesoporous silica.17. Huo. Several pathways are possible depending on the identity of the amphiphile. the mesoscopic silica thin film is a rather simplistic analogue of naturally occurring biominerals. 1999). Our current understanding of the mechanisms behind the development of order is still rather primitive. predictive approaches to mesoscopic silica synthesis must be based on qualitative models.. First. 1992. Significant strides have been made in controlling the micron level morphology of mesoscopic silica materials using soft lithography. the degree of control over the structure at all levels can be improved. Further study of the growth mechanism is required for the development of such models. Hillhouse.2 Towards Control of the Properties At present. 1997. Mechanistic studies of the system have shown the chemistry to be rather complicated. One strategy is to follow the example of nature. Efforts to engineer more complicated features have generally followed two tracks. Progress is expected on two fronts. presence of ternary components and reaction conditions.. Much of our knowledge has come from a phenomenological approach. Just as in biological systems. may provide additional (and perhaps more effective) ways to influence the structure. the organic phase plays a role in determining the structure at multiple length scales.. finer control of the structural features is desired. hierarchical order is present. The design and construction of these materials is one of the most challenging and promising directions of 262 . The growth of mollusk nacre ultimately occurs on the protein surfaces. Mobil Research and Stucky's group at UCSB developed some of the earliest ideas about templating (Kresge. et al. et al. which may not be available to biological organisms. 1997). 17. Orientation of the structural features is imposed through the use of a physical template. relative compositions of the reagents. two things are certain. there is much room for improvement. All of these approaches have been used to orient the internal pore arrangements as well as micron-sized features with varying degrees of success (Trau. Steady progress in understanding the mechanism and controlling the growth has been made. Firouzi. et al.3. Secondly. a class of techniques popularized by Whitesides' group at Harvard University (Zhao. et al.. Although it is not clear at present what exact mechanistic steps are involved. 1994).. et al. At the nanometer length scale. These approaches represent cases where a synthetic processes may benefit from both bio-inspired and more "conventional" design principles. A second strategy for controlling structure involves applying non-biological methods. 1997.. et al. The use of external fields. this includes the ability to orient the pores in arbitrary directions.4 Conclusion Studies of naturally occurring mineral composites with mechanical properties far superior to pure minerals have revealed that cooperative hierarchical structure is one way to attain improved material properties. produce materials with a single orientation of pores. The effects of electrical. magnetic and shear fields on fluids has been the subject of much experimental and theoretical work. Furthermore.

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a large number of interfaces or grain boundaries are created. or magnetic properties different from their bulk materials and the individual atomic constituents. the nature and the number of atoms surrounding an interfacial atom can be very different from those of atoms located within the nanograins. Relaxation and reconstruction can relocate interfacial atoms from their bulk-like positions. contain only a small number of atoms tightly bound together by an attractive potential. by definition. we will discuss some recent research efforts in elucidating the relationship between the nanostructure of metal oxide nanophase materials and their electrochromic properties. 266 . In this chapter. electrical. One of the main reasons for this lack of breakthrough is probably due to the limited understanding of the electrical.18. we will discuss electrochromic properties of nanophase metal oxide materials. and electrochemical properties of nanophase materials and the relationship of these properties to the nanostructure of electrochromic materials. In this chapter. nanodomains have a high surface-to-bulk atom ratio. optical. mechanical. Section 18. we will focus our discussion on the synthesis and structural characterization of antimony-tin oxide (ATO) nanophase materials that were recently reported to have enhanced electrochromic properties (Coleman. Atoms located at interfaces or grain boundaries are flexible and dynamic: they interact with and conform to the surrounding environment. and elucidate the origin of the enhanced electrochromism of tin oxide nanocrystallites heavily doped with antimony. discuss a novel device design for fabricating flexible. In Section 18. in Section 18. These nanodomains. Various nanophase materials and their applications have been discussed in the previous chapters. We will discuss. Detailed discussions on the electrical. Thus. printed electrochromic displays. a new design strategy for constructing printed. A unique feature of nanodomains is that a large fraction of the atoms are located on the surfaces of the domains.2 is intended to provide basic background on electrochromic materials and the performance of electrochromic displays. as demonstrated by the significant increase in the number of patents in the last two decades. optical. 1999a).4. their sizes are usually in the range of 1 nm to 100 nm. a nanophase material can be treated as a nanocomposite consisting of at least two phases: one phase is related to the atoms located within the nanograins and another phase is related to the atoms located at grain boundaries or interfaces. Basic knowledge of the properties of electrochromism and electrochromic devices may help the readers appreciate the issues involved in producing commercially successful devices. Nanophase materials often exhibit novel chemical. flexible electrochromic displays using interdigitated electrodes. When these nanodomains are joined to form bulk nanophase materials. The interfacial regions or grain boundaries introduce new electronic or crystal structures. et al. Although great efforts have been put into the development of commercial electrochromic products. Nanophase metal oxide materials for electrochromic displays 18..1 Introduction Nanophase materials generally refer to material systems consisting of interconnected nanodomains or other nanocomponents.3. large-scale applications of electrochromic devices have not yet been realized.

Monk. Ziegler and Howard.g. H+. 1993. Mortimer. A thin film of electrochromic material is then deposited on the OTE by various deposition techniques. 18. shutters. 1982. and electrochromic properties of ATO electrochromic displays will be given in Section 18. and electrochromic devices (Baucke. 1995). 1995.1 Electrochromic Display Device Electrochromic devices are able to change their color reversibly under the action of an externally applied voltage pulse.6.2 Basic Concepts in Electrochromism During an electrochemical reaction.. 1994. Na+. Granqvist. Figure 18. etc. 1991. windows. We will conclude this chapter with a brief summary in Section 18.) and electrons while the electrolyte layer should have zero conductivity for electrons but very high conductivity for small ions. An electrochromic device is essentially a rechargeable battery with the electrochromic electrode separated by a solid. Dautremont-Smith. the electrochromic layer should be a good conductor for both small ions (e. or liquid electrolyte from a charge-balancing counter-electrode. 1995). electrochromic materials. An ionically conductive electrolyte is then incorporated between the counter electrode and the electrochromic layer. The OTE supplies electrons to the electrochromic layer.1 illustrates the essential components of a conventional electrochromic display with a "sandwich" configuration of electrodes. 1993. et al. electron-transfer reactions often change the optical absorption properties of the reacting compounds. gel. Figure 18.1 Schematic illustrating the conventional "sandwich" design of reflective electrochromic display using optically transparent electrode (OTE) and glass support.. Tin-doped indium oxide (ITO) is the most commonly used material as the OTE. Mastragostino. Deb. Ideally.structural. and electro-optical data storage devices (Monk. Li+.2. 1997. The front panel usually consists of a thin film of optically transparent electrode (OTE) deposited on a glass support. 18. Many inorganic and organic compounds exhibit pronounced electrochromic behavior that makes these compounds interesting for developing commercially viable electrochromic displays. 1995. et al. Electrochromism refers to the phenomenon of reversible color changes induced in materials by electrochemical processes.. Most of the following material in this section is drawn from the extensive literature on electrochromism. 267 . Scrosati.5.

highly mobile ionic species (e.2.. Thus. To ensure charge neutrality. 1993. 1994. the ion-insertion process induces changes in the electronic distribution of the host electrochromic material. Li+. The injection of electrons shifts the Fermi energy of the electrochromic material and. 1993.. Scrosati.When an external potential is applied between the working and counter electrodes. thus. Based on their mechanism of coloration. 18. Although details of the electrochromic processes depend on the specific materials used. et al. electrochromic materials can be broadly grouped into two categories: ion-insertion materials change color 268 . Electrochromic materials are currently attracting much attention because of their fascinating fundamental electrochemical properties as well as their potential commercial applications.g. A comprehensive discussion on inorganic and organic electrochromic materials can be found in a recent book on electrochromism (Monk. it is generally believed that the coloration occurs as a result of the injection and trapping of electrons in the electrochromic materials.2 Electrochromic Materials Materials that undergo color changes during an electrochemical redox reaction are called electrochromic materials. the charge or discharge of this electrochemical cell induces color changes in the electrochromic layer. When an appropriate potential is applied between the front OTE and the counter electrode. however. Many chemical species exhibit electrochromism. Mortimer. Granqvist. 1997). the insertion of one positive ion into the electrochromic material must be accompanied by the injection of a balancing electron into the same material. 1995) and in several recent review articles (Mastragostino.) in the electrolyte is inserted into the electrochromic material. The modulation of the optical properties of electrochromic devices is largely determined by the capacity of the electrochromic materials for charge injection and expulsion. changes its optical absorption properties.

the injection and extraction of electrons and metal cations play a critical role in determining the electrochromic performance of tungsten trioxide electrochromic devices. and the bandgap is so wide that the material appears transparent in its pristine state. Although the detailed electrochromism is still not well understood. and n is usually an integer that depends on the particular type of metal oxide of interest. The insertion of electrons has the effect of lifting the Fermi energy 269 . Upon electrochemical reduction. WO3. Organic systems such as bipyridilium and electroactive conducting polymer systems have also received great interest (Mastrogastino.through reversible insertion of ions and injection of electrons. α is a fractional insertion coefficient. Although the details of the electrochromic processes are not known on a nanoscopic or atomic level. 1969). 1995. The most classical example of this type of ion-insertion metal oxide materials is tungsten trioxide. et al. intervalence electron transfer can occur between W5+ and W6+ sites. e. 1995). electrochromic metal oxides have been the most intensively studied ion-insertion materials. Mortimer. With the use of Li+ containing electrolytes. the ion-insertion or ion-extraction processes of electrochromic metal oxides can often be schematically represented by where Me represents a metal. With the assistance of a photon. 1994). For heavily disordered tungsten trioxide films. 1967). giving an intense optical absorption. Thin films of tungsten trioxide are usually transparent or pale yellow. reversible electrodeposition materials produce color change through the plating of thin films onto and stripping of thin films from an OTE (Ziegler and Howazd. the Fermi energy lies in the gap between the valence and the conduction band. An electronic band theory has also been proposed to explain the electrochromic mechanisms of various metal oxide systems (Granqvist. thus. Ever since the discovery of the electrochromic behavior of thin films of tungsten trioxide (Deb. Many thin films of transition metal oxides can be electrochemically switched to a non-stoichiometric redox state that has an intense electronic absorption band due to optical intervalence chargetransfer (Hush. A± represents a singly charged ion. some tungsten sites with an oxidation state W5+ can be created.is the charge of an electron. 1997). the electrochemical reaction can be written as This photon-assisted intervalence transition between lattice sites of different oxidation states has been used to explain the electrochromic behavior of most transition metal oxide systems. 1993. depending on how the films are prepared. all the tungsten sites have an oxidation state W6+.. Monk.

Light comprising all visible electromagnetic wavelengths (420–700 nm) appears white to our eyes. and the film thickness of the electrochromic layer. thus making the material more electronically conductive and intensely absorbing of photons by free electrons. 18. plus the scattering effect of particulate materials. an integrated (over visible wavelengths) contrast ratio is often used for white light illumination.2. Diffusely reflected colors from a display device result from absorption of visible light with certain wavelengths. Oi. The contrast ratio often depends on the specific wavelength of the illumination system. The time required for an electrochromic device to change from its bleached state to its colored state is called the device's response time. microstructure. Absorption of photons by a solid material depends on the band structure of the material and can be measured by a spectrophotometer. The contrast ratio of a display is defined as the ratio of the intensity of light diffusely reflected from its bleached state to that of light diffusely reflected from its colored state. and electron diffusion from the electrode into the electrochromic layer. a contrast ratio is often used to quantitatively measure the degree of color change or photon absorption. 1980. For electrochromic device's.2. diffusion of ions into the electrochromic material. Since the electrochromic process involves migration of ions in the electrolyte. a contrast ratio with as high a value as possible is desired.3 Perceived Color and Contrast Ratio The color we see from an object is a subjective visual impression involving retinal responses of our eyes to particular wavelengths of the impinging electromagnetic waves. for practical devices. 18. For successful commercial applications.4 Coloration Efficiency and Response Time The optical absorption properties of an electrochromic display are related to the injected charge per unit area of the active electrode. The coloration efficiency is a measure of the performance of the electrochromic material. usually a few seconds or longer. Under white light illumination. The coloration efficiency is defined as the ratio of the change (between the colored and bleached state) of optical absorbance to the charge injected per unit area of the display electrode. the response time is.upward into the conduction band. the perceived color of a display is related to the complementary color of the light that the electrochromic material absorbs. in practice.5 Write-Erase Efficiency and Cycle Life 270 . The optical absorbance is defined as the log of the contrast ratio. 1986). However. Therefore. electrochromic devices exhibiting much faster response times were reported in the literature (Haranahalli and Dove. 18. it depends on the chemistry. Diffuse reflectance spectroscopy is often used to measure the absorption spectrum of reflection displays although complications may arise from light scattering by microparticles or grains.2.

1967). et al.. 1982). For successful commercial applications. is closely coupled to the response time. conductive electrodes are usually used in electrochromic devices.3 Nanophase Metal Oxide Electrochromic Materials Transition metal oxides. 1995). These transition metal oxides possess unique structural configurations. IrO2. the initial write-erase efficiency should approach 100% or as high a value as possible. 1990). 1986). the physical structure and the chemistry of the electrochromic device should not change after many cycles of electrochemical reactions. or dip-coating (Hinokuma. etc. The coexistence of ions with different oxidation states in a transition metal oxide makes it possible for an electron to be excited from one site to an adjacent site. or both.The write-erase efficiency of an electrochromic display refers to the percentage of the originally formed color that can be subsequently bleached by a reverse potential. 1983. When an electrochromic device is continually cycled between its bleached and colored states. chemical vapor deposition (Donnadieu. 1986. their electrical and optical properties have been extensively reviewed (Hamberg and Granqvist. ITO films are rarely used as the primary electrochrome. Calvert. et al. edge sharing. we will not review them here. 1992). Thin films of metal oxides deposited on transparent. electrodeposition (Bendert and Corrigan. Previous studies show that ITO films exhibited little or no optical change in the visible region under typical conditions of operating electrochromic displays (Brotherston. it can be expressed as the ratio of changes of absorbance after one complete redox reaction cycle. instead we will focus our discussion on some recent development in using nanophase. Co2O3. the coloration efficiency progressively deteriorates and device failure eventually occurs as a result of physical changes or chemical reactions. Granqvist. The cycle life is a measure of the long-term stability of an electrochromic device. Because of its inherently weak electrochromism and quasi-reversible ion-insertion processes.. presumably due to optical intervalence charge transfer occurring in mixed-valence compounds (Hush. A major goal for device design and fabrication is to maximize the device's cycle life. sputtering (Suzuki and Mizuhashi. heavily doped. however.. Thin films of tin-doped indium oxide (ITO) are widely used as semiconducting. semiconducting metal oxide materials for electrochromic displays. 1989). 1956). Rh2O3. 18. the write-erase efficiency slowly degrades because of structural or chemical changes occurring within the electrochromic device. Since there is extensive literature on the electrochromism and the preparation methods of these metal oxide materials. Various strategies have been proposed to increase the write-erase efficiency of electrochromic devices (Wrighton and Bookbinder. accompanied by the absorption of a photon.. The write-erase efficiency is a measure of the reversibility of the electrochemical reaction and. sol-gel process (Hensch and West. 1993). for practical applications. V2O5. In practice. et al. MoO3. 271 . comprising MeO6 octahedral building blocks connected either by corner sharing. These films can be prepared by a variety of techniques including thermal evaporation (Holland. optically transparent coatings or electrodes for the construction of electrochromic devices. such as WO3. exhibit intense optical absorption. Ideally. NiOx. 1988).

we chose to use wet chemical techniques to produce large-scale ATO nanophase materials. temperature. Although many factors affect the perceived contrast of reflective electrochromic displays.. The knowledge gained from the study of ATO nanophase materials can be equally applied to ITO or other doped metal oxide nanophase materials. the specific method of mixing. A solution of SnCl4 · 0. additives. silica. the heater is turned off. reaction time. The advantages of using wet chemistry in making nanophase materials include the following: control the mixing of different precursors at the molecular level. 1979.Antimony-doped tin oxide (ATO) materials have many interesting and useful properties for industrial applications: ATO particles or powders are used as oxidation catalysts (McAteer. 1981).1 Synthesis of Supported ATO Nanocrystallites To better control the synthesis processes of nanophase materials and to keep the cost for mass production as low as possible. The mixed Sb/Sn chloride solution is added to the alumina powder solution over a period of about 45 min from a burette with concurrent addition of 15% sodium hydroxide solution from another burette to keep the pH value of the mixture at 0. we describe a detailed procedure of how to make tin dioxide nanocrystallites heavily doped with antimony (43 mol/% Sb) and finely dispersed onto alumina particulates to make a powdered material consisting of 75 wt% of ATO and 25 wt% of alumina. In the following.0. stoichiometry. Figure 18. After the Sb/Sn chloride solution is completely added to the alumina solution and the neutralization is complete. et al.0 g) in deionised water (20 mL) is mixed with SbCl5 (25. and. The wet chemical methods usually start with molecular precursors in a solution form to make a final condensed phase. and precipitation of amorphous or crystalline nanoclusters. growth.8–1.. and control the solution homogeneity during reaction...2 illustrate the sample preparation procedure.. pressure. and components for solar cells and gas sensors (Oyabu. ATO and ITO nanophase materials exhibit surprisingly high level electrochromism (Coleman. 1999a). antistatic pigments. et al. and the mixture. when ATO or ITO nanocrystallites are dispersed onto transparent or light-colored oxide powders such as titania. concentration. However. et al.2. in some cases.5H2O (40. Similar to ITO films.0 g) in concentrated HCl (20 mL).3. alumina. Alumina powder (10. The nature of the condensed phase depends on the physicochemical conditions such as the type of precursor.0 g) is stirred in deionised water (200 mL) in a beaker heated to 90°C. et al. the pH value of the final mixture is adjusted to 2. 18. the presence of additives or surfactants. 1982. is allowed to cool down for 3 h. nucleation. control the reaction kinetics by choosing the right solvent. 1983). we found that the enhanced electrochromism of supported ATO or ITO nanocrystallites is related to the nanostructure of the synthesized nanophase materials (Liu. 272 . Berry. and temperature. 1994). Since the synthesis processes and the electrochromism of ITO nanophase materials are similar to those of ATO nanophase materials. etc. solvent system. 1998. 1998). the use of light irradiation. still being stirred. thin films of ATO materials exhibited very weak electrochromism (Orel. we will focus our discussion only on ATO systems. Chopra.

The white. 18. solid precipitates are then filtered off. washed with deionised water.4).2 Characterization of Supported ATO Nanocrystallites 273 .3.Figure 18.2 Schematic illustrating the synthesis process of antimony-tin oxide nanophase materials using wet chemistry method. the sample is removed from the oven and is allowed to cool quickly in air. The final light-gray powders are then mixed with polymer binders to produce inks suitable for printing (see Section 18. ATO nanophase materials prepared by using antimony pentachloride precursors may give better switching properties than do those prepared by using antimony trichloride precursors. A sequential addition of Sb and Sn solutions to alumina or other light-colored metal oxide supports did not give satisfactory electrochromic performance. The dried powders are then calcined in an open ceramic crucible at 600°C for 3 h. and dried at 60°C in a vacuum oven for > 3 h. Our studies showed that it is critical to simultaneously precipitate Sb and Sn molecular species to optimize the contrast ratio of ATO electrochromic displays. At the end of the calcination.

The synthesis strategy is to uniformly coat ATO nanocrystallites onto light-colored oxide powders. clearly revealing the coating of ATO nanocrystallites onto the large TiO2 particulates. The purpose of using powder supports is similar to that of supported metal catalysts: to increase the total surface area of ATO nanocrystallites that can be easily accessed by ionic species in the electrolyte. preferably. the oxide powders should be completely coated with one or. such as alumina powders or silica shells. more layers of conductive ATO nanocrystallites. High-resolution backscattered electron image.3(a) illustrate the spatial arrangement of ATO nanocrystallites and titania particulates.4 shows a high-resolution transmission electron microscopy (HRTEM) image of a cross-sectional 274 . Figure 18. Therefore. To understand the atomic structure of the ATO nanocrystallites and their interactions with the TiO2 support. to ensure a good electrical conductivity of the electrochromic ATO-support materials. Fig. and silica.3 (a) Coating of antimony-tin oxide nanocrystallites onto light-color oxide supports such as titania. Figure 18.3(b) shows a high-resolution backscattered electron image of a cross-sectional sample of ATO-TiO2 powder. The oxide supports may not be conductive. Figure 18. (b) Antimony-tin oxide supported on titania powders reveals coating of ATO nanocrystallites onto titania particles. alumina. 18.

275 .sample of ATO-TiO2 powder as that shown in Fig. flexible electrochromic displays. low conductivity on plastic substrates.4 Construction of Printed. rigid device because of the use of glass support. While such a design can give desired performance. The coating thickness is in the range of 5 nm to 50 nm and the sizes of the ATO nanocrystallites range from about 2 nm to 10 nm.5. HRTEM images of ATO nanocrystallites supported on other oxide particulates showed similar results. and the annealing temperature.4 High-resolution transmission electron microscopy image of ATO nanocrystallites attached to titania microparticles. and electrochemical instability leading to corrosion. it suffers several drawbacks: high cost. the solution pH value. To synthesize high-performance ATO electrochromic nanophase materials. The effects of these factors on the contrast of electrochromic displays will be discussed in Section 18. difficulty in fabricating sophisticated display designs. To overcome these difficulties and to produce large area. There is no preferential crystallographic orientation relationship among the ATO nanocrystallites or between the ATO nanocrystallites and the crystalline TiO2 microparticles. we need to optimize the Sn/Sb ratio. The amorphous material in the image represents the structure of the resin used for embedding the ATO-TiO2 powder. 18. The sample was prepared by ultramicrotming ATO-titania powders embedded in resin. the mixing of Sn and Sb molecular precursors. 18.3(b). Figure 18. especially in aqueous systems. Flexible Displays Using Interdigitated Electrodes The conventional method of fabricating electrochromic displays utilizes a "sandwich" configuration as illustrated in Fig. Various sizes of ATO nanocrystallites are tightly coated onto the TiO2 microparticles and the ATO nanocrystallites are interconnected. 18.1.

Figure 18. Figure 18. 18.5(a) illustrate the cross-sectional view of a display consisting of several layers of printed materials. and (b) the cross-sectional view of a printed electrochromic display showing the Ag/C contacts and the ATO-TiO2 electrochromic layer.5 Schematic illustrating (a) "side-by-side" design of a reflective electrochromic display using interdigitated electrode approach (low magnification backscattered electron image).. completely covering the silver-carbon layer to provide corrosion protection.we developed an interdigitated electrode approach by using low cost printing and coating processes (Coleman.4. a layer of carbon ink is printed. Then. 1999b). et al. 276 .1 Design Strategy The design objective is to print the display on flexible polymer films using commercially viable conductive inks in an interdigitated electrode structure. An appropriate circuit can be designed and screen-printed onto a polymer film with silver-carbon ink as working and counter electrode contacts.

The electrochromic material can be mixed into. high ionic conductivity of the electrolyte is required to maximize current flow through the desired path. the display device is ready to operate. 18. Figure 18. ATO-TiO2 particulates. Figure 18. After printing the conforming carbon layer. especially with electrolyte that diffuses into the electrochromic materials. Ionic current flow through the electrolyte completes the electrical circuit. Ag/C electrodes.5(a). the ATO coated TiO2 particulates.5(b) shows a backscattered electron image of the cross-sectional view of a display device consisting of Mylar support.6(a) shows a photograph of a printed word display. and an ATO-TiO2 electrochromic layer. or printed on top of. electric current moves vertically through the conductive metal oxide dispersion to the interface between the electrochromic material and the gel or liquid electrolyte.6 Photomicrographs of a printed electrochromic display show the exposed electrodes (a) and the same area after covered with the ATO-TiO2 electrochromic layer (b). Figure 18. After a gel-electrolyte layer is pressed onto the electrochromic layer and sealed with a transparent polymer film. Electrochromic process or color change takes place in this interfacial region. The combined thickness of the electrochromic layer and the conductive metal oxide dispersion layer is less than 50 µm. the display may deteriorate quickly and might not maintain a long cycle-life. Low-voltage field-emission SEM image (c) shows the highly porous ATO-TiO2 surface layer. the connecting circuits are then covered with an insulating material.6(c) shows a low-voltage. The actual electrode surface is then printed with light-colored conductive metal oxide powder dispersed in a polymer binder. these patterns can be transformed into displays by using specialized screen-printing technology with a high production rate and low cost.Without the protection of the conforming carbon layer. This leakage current can be further reduced by printing a thin layer of insulator between the working and counter electrodes as illustrated in Fig. Electromigration of silver microcrystals may occur under prolonged use of the display. When an external voltage is applied between the working and the counter electrodes. Figure 18. Figure 18. For this "side-by-side" display design to work efficiently.6(b) shows the same area after printing a layer of ATO-TiO2-polymer electrochromic ink. revealing the uncovered Ag/C working and counter electrodes and the insulator layer. and the polymer binder. the conductive metal oxide materials. 277 . then the leakage current within the metal oxide dispersion layer can be minimized. and the polymer binder. the display device will be degraded. A layer of an aqueous gel electrolyte is then put down before the whole system is sealed with a transparent polymer film. When silver microcrystals interact with other components. If the interelectrode spacing is kept significantly larger than the thickness of the metal oxide coating layer. revealing the surface morphology. covering the area of active display. secondary electron image of the ATO-TiO2 layer. Sophisticated patterns can be designed using commercially available graphic design programs.

A typical material may comprise antimony-doped tin oxide crystals dispersed onto inert. Those materials 278 . 1997). et al. Conducting Electrodes With the "side-by-side" interdigitated electrode configuration. light in color. electrochemically deposited copper. 2. carbon or graphite ink. Powders of conductive metal oxides dispersed in polymer binder solutions can meet these criteria. 4.18.4. photo-patterned aluminum. The stability of these pigment coatings towards aqueous electrolyte is acceptable for commercial applications. these materials are susceptible to overreduction and loss of conductivity when an excessive potential is applied. and sputtered gold. However. can be used. Mortimer. light-scattering TiO2. commercially available silver or silver-carbon inks give the best performance. conducting polyaniline. Insulating Materials To assure easy printing with acceptable resolution.. Electrochromic Layer Many organic or inorganic electrochromic materials are available (Monk. 1995. We screened a variety of materials including silver and silver-carbon ink. conductive metal oxides. commercially available UV-curable acrylated polyols can be used as insulating materials. Electrochromic materials that are soluble in aqueous electrolytes can be used.2 Materials Selection 1. for example. Many light-colored conductive pigments. Conducting Metal Oxides The electrode surface layer should be conductive. electroless nickel. the material should be easily configured and formulated into printable inks. To obtain a combination of good conductivity and ease of printing into sophisticated circuitry with fine resolution. and stable both chemically and electrochemically under operating conditions. In addition. 3. the patterned conducting layer on the polymer support acts as both the working and the counter electrode.

7(c) show the same word display but with the polarity of the applied voltage switched. can be used to fabricate large area. To minimize the effects of field gradients on ionic conduction and to keep the electrolyte resistance as low as possible. 18. and poly-AMPS (poly [acrylamido {methylpropane sulfonic acid}]) are often used as thickening agents. Figure 18. since nanophase ATO-oxide powders display significant electrochromic effect in neutral electrolytes such as aqueous sodium sulfate solution. low cost. A simple printing process. potassium chloride. lithium bromide. liquid electrolytes. such as aqueous salt solutions. et al. heptyl viologen and formulations of Prussian Blue with or without incorporated pigments) as well as the newly discovered ATO. chalky printing layer. and metal ions which can be electroplated such as bismuth (III).4. and polyaniline can be either coated onto the metal oxide surface layer or coated onto the conductive pigment powders prior to being formulated into inks. It is also possible to incorporate fluorescent pigments into the formulated inks to produce bright-colored displays (Coleman. and calcium chloride. g. Pigment-to-binder ratio is an important factor in optimizing the properties of the inks.. 1999b). are preferred. Some commercial polyester films (e. However. After screening many binder-solvent systems. The following hygroscopic salts are frequently used: lithium chloride.include the following: methyl viologen. or even longer than. potassium formate. With a pulsed external voltage. and good water barrier properties.. 279 . an inert. Mylar) can be used because of their excellent transparency. 1998.5 V. Higher binder levels give increased electrical resistance while lower binder levels give a less stable. transparent film is used to seal the display to minimize the evaporation of water present in the electrolytes. heptyl viologen. using inks of powdered materials. commonly used in the conventional "sandwich" design. et al. 1999b). we can use ATO nanocrystallites dispersed onto light-colored powder supports as the conductive electrode as well as the electrochromic layer. Conventional electrochromic materials (e.7(a) shows a word display (neutral state) printed with ATO-silica nanostructured materials as the electrochromic layer. 6.7(b) and 18.g. We have demonstrated that many types of devices with sophisticated designs and a range of colors can be fabricated (Coleman. Ink Formulation Since we intend to fabricate the electrochromic displays by an inexpensive printing technology. we selected a fluoroelastomer (Viton) dissolved in 2-butoxyethyl acetate. Insoluble electrochromic materials such as Prussian Blue. the path of ion migration in the electrolyte may be as long as. Hydroxyethyl cellulose. We typically use an electrolyte that contains a combination of polymeric thickening agent and hygroscopic salt. it is crucial to formulate the powdered materials into conductive inks with excellent printability. poly (xylyl viologen)-poly (styrenesulfonate). ITO. flexible electrochromic displays with interdigitated electrodes. Sealing Film Since a liquid or gel electrolyte is usually used in the construction of the reflective electrochromic display. or other nanophase metal oxide materials can be easily formulated into printable inks and give excellent device performances.. Figure 18. The externally applied voltage was 1. half the combined width of both the working and the counter electrodes. Electrolyte With the "side-by-side" electrode configuration. 5. 7. flexibility.. polyacrylic acid. these flexible displays can be cycled many times with high contrast.3 Display Examples The "side-by-side" design of electrochromic displays eliminates the use of expensive transparent electrodes.

5 V for (c). Only half of the numerical display was activated to demonstrate the performance and the active control of printed. The applied potential was 0.7 Printed electrochromic word displays using ATO-silica powders.8 Seven-segment electrochromic numerical display. +1. Figure 18. 280 . and -1.Figure 18.8 shows another example of a printed seven-segment numerical display.5 V for (b).0 V for (a). reflective displays. Figure 18.

and long cycle life. the types of support used. high write-erase efficiency. we need to understand the factors that affect the contrast ratio of reflective.5 Contrast of Printed Electrochromic Displays Using ATO Nanophase Materials Commercially viable electrochromic devices require electrochromic materials having high contrast-ratio.The contrast of reflective displays depends on many parameters including the ATO loading. high coloration efficiency. is the most important parameter for evaluating the performance of a commercial electrochromic display. 18. and the spatial distribution of the antimony containing species. the average size of the ATO nanocrystallites. 281 . Therefore. Detailed discussions on how to accomplish the multi-parameter optimization process and to select the appropriate parameters are beyond the scope of this chapter. The contrast ratio. fast response time.9. the oxidation state(s) of the incorporated antimony ions. the doping level of antimony. to optimize their performance. however. In the following. we will discuss in detail how these factors affect the perceived contrast of electrochromic displays. we will primarily focus on how the nanostructure of the synthesized ATO-support nanophase materials affect the observed contrast ratio of printed electrochromic displays. In the next section. To enhance the performance of the printed electrochromic displays. The perceived contrast of reflective displays fabricated by the printing technology is influenced by many interacting factors as shown in Fig. 18. printed electrochromic displays. we need to simultaneously optimize all the interconnecting and interacting factors. Both the scattering and the absorption of the incident (white) light determine the contrast ratio.

A similar dependence of contrast ratio on antimony doping was also observed for ATO materials dispersed onto powders of other types of oxides.9 Factors affecting the perceived contrast of reflective. reflective displays depends on the dopant level of antimony in tin dioxide nanocrystallites. The ATO-TiO2 powders were annealed at 600°C for 3 h. 18.10 shows the contrast ratio as a function of antimony doping for display devices prepared with materials consisting of ATO nanocrystallites dispersed onto titanium dioxide powders. printed electrochromic displays using ATO nanophase materials.5. The contrast ratio initially increases. 282 . reaches a maximum value at about 43 mol% of antimony. Figure 18.Figure 18. then decreases.1 Effect of Antimony Doping on Contrast Ratio The contrast ratio of printed.

The resistivity of the ATO nanophase materials critically depends on the doping level.Figure 18. Table 18. reaches a minimum at a value below 10 mol% antimony.1 shows the resistivity of ATO-alumina powders at room temperature as a function of antimony doping. The electrical properties of tin dioxide nanocrystallites are also drastically changed by doping with antimony. The ATO nanophase materials were annealed at 600°C for 3 h.1 Effect of antimony doping on electrical resistivity and color of ATO nanophase materials* Antimony Doping (mol%) 0 10 20 43 * Resistivity (Ω · cm) 3100000 Color Pale Yellow Gray 2 10 Gray Olive 75 wt % ATO-25 wt % alumina.10 Variations of contrast ratio with antimony doping for printed electrochromic displays. Table 18. 600°C/3 h Not only the contrast ratio of the electrochromic displays varies with the doping level of antimony but also the color of the ATO-alumina nanophase materials changes from pale yellow for pure tin dioxide to olive 283 . The resistivity rapidly decreases with low levels of antimony doping. and then slowly increases with further incorporation of antimony into the tin dioxide nanophase materials.

1993). a photon-assisted electron transfer between the different oxidation states can occur. 1993). With low levels of antimony doping.. Egdell.. et al. 1985. Kojima. Kojima. the color change of the ATO nanophase materials. The average size of the ATO nanocrystallites decreases. et al. et al. Reduction of SnO2 material can further increase its conductivity because of the increased level of oxygen vacancies. 1967. 1993. The electrical. the decrease in carrier concentration or the increase in resistivity is probably related to the increase of substitutional doping by trivalent Sb3+ ions (Mulla. The addition of a small amount of antimony to SnO2 results in a dramatic increase in the electrical conductivity. et al. et al. et al.... Chopra.. we examined the nanostructure of the synthesized ATO nanophase materials doped with different levels of antimony. 1980. however. 1980).. 1993). 1976). 1996). et al. Berry and Smith. 1996. Cox. Figure 18.. and structural properties of ATO films and powders have been extensively studied (Carroll and Slack. et al. Mishra. with increasing levels of antimony in SnO2. The change in color with the amount of antimony doping has also been observed in thin films of tin dioxide heavily doped with antimony (Kojima. resulting in intense photon absorption (Robin and Day. 18. 284 . optical. 1995. some of the Sn4+ ions are replaced by Sb5+ ions. X-ray diffraction (XRD) patterns of the powdered materials with antimony doping levels up to 43 mol% showed that the ATO nanocrystallites have a single Cassiterite crystal structure similar to that of pure tin dioxide. et al. Tin dioxide is an oxygen-deficient n-type semiconductor (Jarzebski and Morton. 1996). 1993). et al. Shanthi. Goyal. 1976. et al. et al. et al. 1993. 1984.11)... some of the Sn4+ ions may be replaced by Sb3+ ions.green for ATO nanophase materials with 43 mol% antimony doping. In a material with mixed oxidation states of the same element.11 Variations of the average size of ATO nanograins with antimony doping. Miyata and Kitahata. et al. 1982. With the addition of more than about 10 mol% antimony to thin films of SnO2. 1986). et al. Not only the average size of the ATO nanocrystallites becomes smaller but also the size distribution becomes narrower with increasing antimony doping.. 1993... et al. resulting in a semiconductor with a low temperature dependence of the conductivity (Shanthi. At very high doping concentrations. 1984. 1993. The presence of a mixture of Sb5+ ions and Sb3+ ions in the SnO2 lattice is responsible for the blackening of ATO thin films with heavy antimony doping (Kojima. For thin films of ATO materials. the electrical resistivity increases significantly (Kojima. To understand the effect of antimony doping on the contrast ratio of the ATO electrochromic displays. the increase in conductivity or in carrier concentration with low amount of antimony doping is attributed to the substitutional doping by pentavalent Sb5+ ions (Goyal.. Caldararu... and the change of the electrical resistivity. however. The change in color is related to the increased absorption of photons by the ATO nanophase materials. Kojima.8 nm for ATO materials with 43 mol% antimony doping (Fig. 1983. however. from about 15 nm for pure tin dioxide to about 3.

shows HRTEM images of SnO2 and ATO nanocrystallites prepared by annealing SnO2 and ATO (43 mol% Sb + 57 mol% Sn) precursors at 600°C for 3 h. Figure 18.12 High-resolution transmission electron microscopy images of (a) pure tin dioxide sample and (b) tin dioxide with 43 mol% antimony doping.12(a) and (b). 285 . All the crystallites present in the ATO material have a single rutile-type structure indistinguishable from that of pure SnO2 nanocrystallites. The samples were annealed at 600°C for 3 h.HRTEM images also clearly showed that under the same annealing conditions the average size of ATO nanocrystallites decreases with increasing antimony doping. respectively. Antimony inhibits the growth of tin dioxide crystallites. Figure 18.

However.13. With increasing antimony content. 18. then decreases with further antimony doping. It is interesting to note that even with a doping level as high as 43 mol% there were no distinctive antimony oxide phases observed in the ATO nanophase materials. Since HRTEM images showed that almost all the ATO nanocrystallites are aggregated to form large agglomerates with many grain boundaries and triple-junction regions. the high surfacearea of the ATO nanophase materials suggests that the highly disordered grain boundary or triple-junction regions are easily accessible to small ions. The presence of many grain boundaries also makes more ATO sites accessible to charge injection and expulsion. the lattice constants slightly increases. Fig. Because the ionic radius of Sn4+ is larger than that of Sb5+ but smaller than that of Sb3+ (Shannon. 1976). Surface area measurement showed that the heavily doped ATO nanophase materials have a total surface area as high as 40 m2/g. resulting in a faster response time. especially at the grain boundaries and triple-junction regions. the initial increase in the lattice constants seems to suggest that with low levels of antimony doping (<10 mol%) the amount of substitutional doping by Sb3+ also increase with the doping level. The variations of lattice constants of the Cassiterite ATO nanocrystallites with antimony doping are shown in Fig. 18. The presence of many grain boundaries facilitates a fast diffusion of small ions into and out of the electrochromic ATO layer. resulting in a higher coloration efficiency. These highly disordered interfacial regions may support a high concentration of randomly distributed antimony cations. 286 .12(b) clearly shows that there exist highly disordered materials around the ATO nanocrystallites.Both the XRD and the HRTEM results clearly show that the presence of antimony in the precursor materials inhibits the growth of the SnO2 nanocrystallites during the annealing process.

With increasing levels of antimony doping. With low levels of antimony doping. in a mixed-valence compound such as antimony dioxide. more and more Sb3+ ions are created and preferentially located at the grain boundaries while an increasing amount of Sb5+ ions are located within the ATO nanocrystallites. Skapski and Rogers. Therefore. With increasing levels of antimony doping.13 Variations of lattice constants of antimony-tin oxide nanocrystallites with doping level: a-axis (a) and c-axis (b). the decrease of the lattice constants can be attributed to the increased amount of Sb5+ ions and the decreased amount of Sb3+ ions within the ATO nanocrystallites. when the ATO nanocrystallites become so small that the trivalent antimony ions can be preferentially segregated to the grain boundaries or surfaces of small particles (Pyke.10 can now be explained as follows. 1964. Therefore. 1965). The variations in the contrast ratio with antimony doping shown in Fig. both Sb3+ and Sb5+ ions are present within individual ATO nanocrystallites and both Sb3+ and Sb5+ ions are surrounded by six anions in octahedral coordination. 18. the ATO nanocrystallites becomes smaller and smaller. 1978). With high levels of antimony doping (>10 mol%). the total number of grain boundaries increases. the average size of the ATO nanocrystallites becomes smaller. Since grain boundary scattering and ionized impurity scattering play a major role in determining the carrier mobility in doped semiconductor materials.. Since Sb3+ prefers threefold or fourfold coordination. the increase in resistivity with high levels of antimony doping may be attributed to the significant increase in the number of grain boundaries and Sb3+ ions at these boundaries. the Sb5+ ions prefer sixfold octahedral coordination while the Sb3+ ions prefer fourfold pyramidal coordination (Rogers and Skapski.Figure 18. the trivalent antimony ions substituted on the tin sites in the rutile-type ATO nanocrystallites are not in a preferred coordination. et al. a charge balance on the ATO nanocrystallites requires the presence of both Sb3+ and Sb5+ ions. However. with increasing amount of antimony doping. the total surface area of accessible sites increases. However. 287 .

All these factors contribute to the observed decrease in contrast ratio for antimony doping levels higher than about 43 mol%. Figure 18. The contrast ratio first increases with increasing temperature. 18. The presence of many grain boundaries may also introduce interface states that can be drastically modified by the presence of Sb3+ ions.14 shows the variations in contrast ratio with annealing temperature for displays made with ATO nanocrystallites (43 mol% Sb + 57 mol% Sn) supported on alumina powders. When the ATO nanophase materials become highly disordered or amorphous-like. antimony may act as a glass network former in stead of as a dopant in crystalline tin dioxide.5. more and more antimony ions are located at the grain boundaries. The photon assisted intervalence transition between the Sb3+ ions and the Sb5+ ions gives the black color of the ATO electrochromic display in the colored state as shown in Fig.14 Variations of contrast ratio with annealing temperature for printed electrochromic displays. 288 . and the conductivity of the ATO nanophase materials decreases rapidly. the average size of the ATO nanocrystallites becomes very small. Because of the preferential segregation of Sb3+ ions to the grain boundaries during the annealing process. All these factors contribute to the observed increase in contrast ratio with increasing antimony doping. the injection of electrons will further shift the Fermi energy to the conduction band. there are more Sb5+ ions than Sb3+ ions within individual ATO nanocrystallites.2 Effect of Annealing Temperature on Contrast Ratio The contrast ratio of the electrochromic displays also crucially depends on the annealing temperature of the ATO precursor materials. Figure 18. 18. In the colored state. The increase in contrast ratio with increasing antimony doping for doping levels <43 mol% is related to the increasing number of Sb5+ ions in the ATO nanophase materials. We found that the ATO materials that gave maximum contrast ratio should contain about 43 mol% antimony and be annealed at 600°C for 3 h. Upon electrochemical reaction.7(b). more Sb3+ ions may be generated within the ATO nanocrystallites. When the antimony content is increased to over 43 mol%. disordered antimony oxide domains may be formed. reaches a maximum value at about 600°C. and then decreases with further increase in temperature. antimony ions may be incorporated in the glass network with most favored coordination.and the total number of Sb5+ sites within individual ATO nanocrystallites also increases. the ATO nanophase materials are highly disordered. The precursor materials comprise 75 wt% ATO (43 mol% Sb and 57 mol% Sn) and 25 wt% alumina. Since highly disordered or amorphous materials do not have the constraints imposed by the long-range periodicity of crystalline materials. The intervalence optical transition between the Sb3+ ions and some Sb5+ ions gives the gray or slightly dark gray color of the ATO electrochromic display in the bleached state.

Figure 18.The electrical properties of the ATO powders not only change with antimony doping but also vary drastically with the annealing temperature. then slowly decreases. 289 .46 × 106 Ω · cm at about 250°C.15 Variations of electrical resistivity with annealing temperature for ATO nanophase materials (43 mol% Sb and 57 mol% Sn). rapidly decreases to 123 Ω · cm at 450°C.45 × 106 Ω · cm. The resistivity of the precursor material is about 1. With increasing annealing temperature.15 shows the resistivity of the ATO powders as a function of annealing temperature. the resistivity reaches a maximum value of 16. Figure 18.

17 shows a series of HRTEM images of ATO nanophase materials annealed at different temperatures. The precursor materials comprise 75 wt% ATO (43 mol% Sb and 57 mol% Sn) and 25 wt% alumina. the ATO crystallites grew significantly (Fig. 290 . 18. the ATO powders contain not only crystallites with a Cassiterite structure but also crystallites of separate antimony oxide phases. To understand the structural evolution of the ATO nanophase materials during the annealing process. The precursor material comprised many domains of nanocrystallites joined by highly disordered. amorphous-like materials. Figure 18.16 shows the average size of the ATO nanocrystallites as a function of the annealing temperature. the ATO nanocrystallites suddenly grow significantly. XRD data also showed that when the annealing temperature is lower than about 750°C the ATO nanophase materials contain a single crystal Cassiterite structure. Figure 18.The color of the ATO powders also changes with the annealing temperature: the precursor materials are off-white in color. Figure 18. and the ATO powders annealed at 1000°C are dark gray. the ATO powders annealed at 600°C are gray. When the annealing temperature is higher than about 800°C. The amount of disordered materials present in the ATO nanophase materials decreased with increasing annealing temperature but the ATO nanocrystallites did not grow significantly at annealing temperatures <750°C.17(d) and (e)).16 Variations of average size of ATO nanocrystallites with annealing temperature. clearly revealing that the average size does not change significantly at annealing temperatures <800°C. At annealing temperatures above 800°C. both XRD and HRTEM techniques were used to examine the nanostructure of ATO nanophase materials annealed at different temperatures. However. however. when the annealing temperature is higher than about 800°C.

the resistivity of the dried ATO nanophase materials may increase.Figure 18. Because the small SnO2 nanocrystallites are separated by the non-conducting amorphous species. (c) ATO nanophase materials annealed at 600°C. (d) ATO nanophase materials annealed at 800°C. the highly disordered materials may contain antimony and other species that are probably non-conducting. 291 . In the precursor sample. (b) ATO nanophase materials annealed at 450°C.17 High-resolution transmission electron microscopy images of (a) ATO precursor sample. the moisture and other organic species present in the powdered ATO materials may evaporate. At low annealing temperatures. the precursor material has a very high resistivity. thus. and (e) ATO nanophase materials annealed at 1000°C.

See Section 18. these materials provide high surface area that allows easy transport of mobile ions across the electrochrome-electrolyte interfaces.3 Other Factors That Affect the Contrast Ratio 18.1 for the discussion on the origin of the enhanced contrast ratio of ATO nanophase materials. 18. Thus. With lower loading level. antimony incorporates into the SnO2 nanocrystallites. At a nanoscopic level. At high annealing temperatures >750°C. The high level of antimony present at the interfaces and grain boundaries inhibits the growth of SnO2 nanocrystallites.5. Even though separate antimony oxide phases were observed in ATO materials annealed at 1000°C. Therefore. there were still Sb5+ and Sb3+ ions incorporated into the large SnO2 crystallites. 292 . the total surface area of accessible sites is significantly reduced. 18. the substrate does not have sufficient scattering to make the bleached state appear bright. the high-temperature annealed ATO materials still have a good conductivity. and the amount of antimony available to provide electron charge carriers is also reduced. An increased level of electronic states at the grain boundaries may also be responsible for the color formation of ATO electrochromic displays. the contrast ratio varies with the loading of ATO nanocrystallites onto oxide powders. 18. the ATO coating onto the non-conducting alumina may not be optimized.14. and then the lightly doped SnO2 nanocrystallites grow significantly. antimony first migrates away from the grain boundaries to form separate and stable antimony oxide phases. The improved electrochromic performance of ATO nanophase materials annealed at about 600°C can be attributed to the formation of nanocrystallites with many antimony-rich grain boundaries. At annealing temperatures <450°C. Incomplete dehydration to form appropriate metal oxide lattices and insufficient oxygen evolution which is necessary for antimony reduction to provide electron charge carriers may also contribute to the observed low contrast ratio. we found that the contrast ratio maximizes with a loading at about 75 wt% ATO (43 mol% Sb + 57 mol% Sn) onto alumina (Fig.5. At very high annealing temperatures. because of the increased mobility. more ATO sites can be quickly accessed during the charge injection and expulsion process. the incorporation of antimony into the SnO2 nanocrystallites and grain boundaries may not be complete. For example.18). With alumina powders as support. The resistivity of the ATO nanophase materials is also too high for electrochromic processes to give a high contrast ratio. most of the antimony atoms diffuse to the grain boundaries of the SnO2 nanocrystallites. the dark-gray color is due to photon-assisted intervalence transitions between Sb5+ and Sb3+ ions located within the large SnO2 crystallites. the contrast ratio decreases with annealing temperature for temperatures >750°C as shown in Fig.3.During annealing at moderate temperatures. The reduction of highly disordered materials around the SnO2 nanocrystallites and the incorporation of Sb5+ ions into the SnO2 nanocrystallites increase the conductivity of the ATO nanophase materials.5. 18.9. the total number of grain boundaries is reduced. Therefore. Beyond this loading level.1 Effect of ATO Loading The contrast ratio of printed electrochromic displays is influenced by many interacting parameters as shown in Fig.

. Figure 18.18 Variations of contrast ratio with ATO (43 mol% Sb and 57 mol% Sn) loading level onto alumina powders. 18.5. et al. The loading of ATO nanocrystallites (43 mol% Sb + 57 mol% Sn) onto the various substrates is 75 wt%.3. 1999b).Figure 18. We have produced electrochromic displays using various powder materials such as titania microparticles. silica shells. and calcium fluoride powders (Coleman. 1999a. 293 . A variety of light-color powder materials can be used as support for ATO nanocrystallites. Figure 18.19 shows the effect of using different substrates on the contrast ratio of ATO electrochromic displays. aluminum borate powders.2 Effect of Substrate The contrast ratio also depends on the types of substrate for supporting the ATO nanocrystallites. alumina powders.19 Variations of contrast ratio with types of substrate. barium sulfate powders.

1 Contrast ratio 2.8 75 wt% ATO-25 wt% alumina.0 11.2. We found that coprecipitation of antimony and tin is crucial to maximizing the contrast ratio of ATO electrochromic displays..1 133. Most of the discrepancies may originate from the different sample preparation methods used to produce the ATO materials. 1982).0 Resistivity (Ω · cm) 6.3 Effect of Precipitation Sequence The structure of antimony-tin oxide with high levels of doping has been the subject of discussion in the literature. Sb (43 mol%) Sn (57 mol%).2 5. Various upper limits of antimony doping for forming homogeneous solid solutions have been reported (Berry.0 6. Cox. 600°C/3 h 294 . 1981.5 3. The electrochromic contrast is clearly better for the "homogeneous" sample where the antimony can make the greatest electronic contribution to material properties. The optical and electrical properties of three samples prepared using the same ingredients but with different precipitation sequence are shown in Table 18.2 Effect of order of metal hydroxides deposition on contrast ratio* Order of deposition Sb First Sb First Simultaneous * Crystallite size (nm) 5.5. Table 18. et al.18.3 3.3.

Homogeneous distribution of high levels of antimony dopant in the ATO nanophase materials is required for optimal electrochromic properties. 18. When tin is precipitated first. 18. thus the smallest crystallites are generated during annealing because of the inhibition of crystal growth by the antimony oxide layer at moderate annealing temperatures.20 High-resolution transmission electron microscopy image of ATO nanophase materials annealed at 600°C for 3 h. we can infer that the antimony and tin did not completely interdiffuse under the annealing conditions (600°C for 3 h).20. This sample has the lowest electrical resistance of all three samples. Figure 18. The precursor materials were prepared by a sequential precipitation process (antimony first). A separate antimony pyrochlore phase was observed which may be responsible for the relatively high electrical resistance.Since all three samples clearly show different properties.5.3. Since the tin dioxide nanocrystallites were not fully doped with antimony. small SnO2 nanocrystallites may be coated with a layer of antimony oxide.1. With antimony precipitated first. partially doped tin dioxide nanocrystallites coated the outside of large antimony oxide particles as shown in Fig. the pH value of the metal cation solution plays 295 .5.4 Effect of pH Value Because the ATO synthesis starts with molecular precursors in a solution form and hydrolysis and condensation reactions occur during the reaction processes. the contrast ratio of the electrochromic display should be low as we discussed in Section 18.

Table 18. and lower contrast ratio of the electrochromic displays. The effect of adding NaCl to the oxide precursor on the contrast ratio and electrical resistivity of the synthesized ATO nanophase materials is shown in Table 18.an important role in determining the structure of the ATO precursor precipitates.3 shows the electrical.8 pH 2 5 7 * Resistivity (Ω · cm) 13 672 1. resulting in the formation of a separate. With increasing pH value. the average size of the ATO nanocrystallites decreases. Sb (43 mol%) Sn (57 mol%). the electrical resistivity increases significantly.4 Effect of adding NaCl to ATO precursors on contrast ratio* ATO crystallite size (nm) NaCl added (%) Resistivity (Ω · cm) Contrast ratio Color 296 . With increasing pH value. structural. Table 18.5. and the contrast ratio of the ATO electrochromic display declines.4.2 3.3 3. 600°C/3 h 18. the color of the annealed ATO powders also changes from dark gray to light gray. sodium ions are exchanged into the ATO nanocrystallites. The preferential aggregation of small NaCl particles along the grain boundaries of the ATO nanophase materials could increase the electrical resistance.6 Color Dark gray Medium gray Light gray Sodium Ion (wt%) 0.2 1.4 2.5 Effect of Adding Salts Since the electrochromic performance of the ATO nanophase materials depends on quick access of ions to the metal oxide sites and the nanostructure of the electrolyte-electrochrome interface. thus.3 Effect of solution pH value on contrast ratio* ATO crystallite size (nm) 5. The addition of salts could also affect the electronic band structure of the interface states and. lighter color of the ATO nanophase materials. As the pH value of the solution is increased from 2 to 7.3. the sodium content increases.5 Chloride (ppm) 842 61 247 Other crystalline phase Ilmenite NaSbO3 75 wt% ATO-25 wt% alumina. electrically insulating ilmenite phase.0 4. HRTEM images revealed the presence of NaCl nanocrystallites in the agglomerates of ATO nanocrystallites.5 1. Table 18. The addition of NaCl to ATO precursors resulted in higher electrical resistance. adversely modify the electrochromic properties of the ATO nanophase materials. and electrochromic properties of these ATO materials. adding salts to the metal oxide precursor could help create ionic pathways during annealing. a series of ATO nanophase materials were prepared with different pH values. To understand the effect of solution pH value on the contrast of the electrochromic displays.3 × 106 Contrast ratio 4.

J. K. References Baucke F..6 Summary Nanophase antimony-tin oxide materials have unique electrochromic properties. printed electrochromic displays can be produced by an inexpensive printing technology. using interdigitated electrodes. P.8 7. 723 (1989) Berry F. Thomas. J. The enhanced contrast of ATO electrochromic displays originates from the presence of Sb5+ ions within individual ATO nanocrystallites: upon electrochemical reaction. Owen. 31 (1996) 297 . Corrigan. 107 (1984) Brotherston I. D. permits the production of large-area displays with sophisticated patterns at a much lower cost than that of the conventional "sandwich" design using rigid. J. 30. Ovenston. 39. Materials Science and Engineering. A. I. The enhanced optical absorption and fast switching process can be attributed to the presence of many grain boundaries.0 1 5 10 * 5. D. R. Smith. R. Solar Energy Materials and Solar Cells. and D. Applied Catalysis. The nanostructure of the synthesized ATO nanophase materials determines their optical and electrical properties. Sprinceana. J. 136. A141.4 Dark gray Dark gray Light gray Light gray 75 wt% ATO-25 wt% alumina. M. 97 (1981) Berry F.0 4.5 12 33 290 5680 6. optically transparent electrodes. J. photon-assisted intervalence transition between Sb5+ ions and Sb3+ ions within ATO nanocrystallites gives the intense dark color observed in reflective ATO electrochromic displays. Flexible. Ionescu.8 4.5 4. Advances in Catalysis. A. G. Sb (43 mol%) Sn (57 mol%). Electrochem. J. Soc. and D. 88. and the high surface area accessible to injected charges. the small size of ATO nanocrystallites. 600°C/3 h 18. The novel "side-by-side" design.. Cao. G. 257 (1995) Caldararu M. Weglicki and J. 285 (1991) Bendert R. Catalysis.5 3. Walls and N..0 4. B10. Z.

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1997). Apart from the band structure. much has been focused on the work done in our Lab. As is well known.19.. leading to quasi-phase-matching or quasi-phase-matched (QPM) frequency conversion more efficient than by a birefringence phase-matching (PM) method (Feng. 1997). such as by the modulation of domain structures. Another DSL. 1997.) has been widely used in the literature. for example. et al. dispersion relation. 1995). which is important for applications such as suppressing spontaneous emission. a periodic elastic composite known as the phononic crystal. has also attracted much interest (Espinosa.. Thus. and the like. especially on coupled nonlinear optical frequency conversion in quasiperiodic structures and optical bistability. compositions. For example. These new materials show many unusual behaviors. Sigalas. the nonlinear optical coefficients can be engineered.. In fact. 19. With the development of modern science and technology. the reciprocal space. 1998). metallic. attention has been paid to phenomena such as Anderson localization and possible applications such as acoustic filters and new transducers (Kushwaha. Associated with the photonic crystal is the variation of dielectric constants. the most studied are the semiconductor and metallic superlattices. (Armstrong. 1962) proposed the idea that nonlinear optical phenomena could be enhanced enormously by the modulation of nonlinear optical coefficients in the dielectric material. may be used in classical wave processes. 1980. research on dielectric superlattices (DSLs) has been possible only recently.1 Introduction Artificial superlattices are engineered microstructures.. The propagation of classical waves in a DSL (classical system) is similar to the electron motion in a periodic potential of crystal lattice (quantum system). Great progress has been made along this direction since then. PPLN. et al. 1994. Since there are reviews of progress in periodic poling methods for second-harmonic generation (SHG) (Houe and Townsend. dielectric. by the modulation of crystallographic orientations and heteroepitaxy structures. In this Chapter. novel laser geometries. phase structures.2 Preparation of DSLs DSLs can be realized by the modulation of microstructures.. which are of fundamental interest in physics and have potential applications in microelectronics. 300 . etc (Joannopoulos. In the past several decades. The modulation parameters may not be restricted to those mentioned above. In dielectric crystals. Brillouin zone. Like bulk materials. etc. The modern technology of crystal growth and microprocessing (Joannapoulos. 1992).. when Bloembergen et al. et al. 1995) and in QPM nonlinear interactions (Byer. et al. PPKTP. research on DSLs for nonlinear optics may be dated back to 1962. et al. the most important physical processes are the propagation and excitation of classical waves (optical and acoustic waves). Such is the case for photonic crystal (Yablonovitch. an overview will be given of the studies on DSLs for nonlinear optical effects. here we prefer to use DSL for these structures. Fejer. they can be divided according to their constituents into several categories: semiconductor.. some ideas in solid state electronics. et al. etc. Ming. 1987). Engineered Microstructures for Nonlinear Optics 19. et al. Although periodically poled (PP) something (for example.

(1982a) in LiNbO3 (LN) crystals with periodic ferroelectric domains (periodic DSL) by the growth striation method. 1995. 1989.. et al. 1982. Wang. KNbO3. et al. Y. 1993a. N. 1997a. 1996. Although Camlibel (1969) measured the spontaneous polarization of LN and LT using a pulsed electric field.. 1989).. Karlsson. et al.. Chen. et al. 1987.. et al. Chen and Risk. Zhu.4 Nb2O6 (SBN).. 1995. et al. et al. et al. et al.. 1984. Q. et al. Meyn. 1996. Chen and Risk..2.1 Schematic diagram of a periodic DSL. L. 1986. it is not easy to reverse their spontaneous polarization at room temperature (Nassau and Levinstein. 1993. Recently. 1996) has attracted much attention due to its capability to fabricate. Wen.2 mm by RTPT. et al. et al... Figure 19. Setzler.. when combined with photolithography. Ming.. et al. et al. 1991. Sr0. 1996a) make it possible to fabricate 1-D. 1980. Zhu. KTiOPO4 (KTP).1 is a schematic of the structure obtained by RTPT. Lu. Lu. et al. et al. 1994. 1985. et al.6 Ba0. Zhu. room temperature poling technique (RTPT) (Yamada. much effort has been paid towards the fabrication of more thicker samples as well as other materials. 1995. 1999. electro-optical effect (Zhu and Ming. 1989. et al. 1997).. et al. RbTiOAsO4 (RTA). Lim. Zhu. 1997. Since then. et al. (1993) who fabricated successfully for the first time a periodically poled LN with thickness of about 0. Ando.. 1995. (Webjorn. et al.. BaTiO3. 1991. 1991. 1965)... et al. 1999). et al... 1986. it was Yamada et al.. 1994. Ito. the atomic-layer-controlledepitaxy and heteroepitaxy (patterned growth by MBE.. 1993.. 1999). et al. 1992) or photorefractive effect (Xu and Ming. Byer. or the use of acousto-optical effect (Feng and Ming. such as LT. Myers. 1996. et al. et al. et al. 1995.1 Preparation of DSLs by Modulation of Ferroelectric Domains The DSL was first realized by Feng (1980) and Ming et al. Y. 1993a. 1997a. Webjorn. much progress has been made towards the fabrication of such a structure either in a bulk material or in an optical waveguide material through a variety of techniques (Feisst and Koidl. et al. 19. 1990.. Ito. Y. Myers.... Wong. Webjorn.. Batchko. b.... Y. domain structures with any pre-designed patterns. Figure 19.. 1994. Karlsson. MOCVD) (Nishizawa. Since the coercive field of bulk LN and LiTaO3 (LT) is very high. Wang. Harada and Nihei. 1999). 2-D and 3-D DSLs.. S. Magel. Below we will describe the preparation of DSL by the modulation of ferroelectric domains and by photorefractive effect. 1982a. the assembly of small dielectric spheres (Wei. 1996a.. Risk and Lau. 301 . Among them. et al. Hadimioglu.. Xue. et al.. Ito. 1994. 1995. et al. b. 1982).et al. etc..

the melt is doped with solutes.. and an internal field that has been attributed to nonstoichiometric point defects. Xu. It was found that polarization reversal by RTPT is as follows (Zhu. Feisst and Koidl. meanwhile a temperature fluctuation is introduced into the solid-liquid interface either through an eccentric rotation or through the application of an alternating electric current. et al. the field is about one thirteenth (Kitamura. Then it grows both forwardly and laterally.. 1982a). Y.. 1996a. Ming. et al.5 wt%. 1989. 1997). b. et al. 1992). a surface dielectric gap. and bulk charges.. since it is easy to grow and is available commercially with high quality. 1986. There is an another type of periodic domain structure where the direction of spontaneous polarization of domains is perpendicular to the domain boundaries. i. Taking LN as an example. while for a sample with periodic electrode on its surface... 1995a. with concentration about 0. 1982a. (1999) used an improved electric field poling technique. 1995. most of the reported domain inversion kinetics in these crystals has been for the congruent composition.. gap regions between the electrodes will be filled by the broadening of the inverted domains... 1998). Chen. 1992). In 1972. The fields for the domain reversal in the stoichiometric crystal are much lower than those for the congruent crystal. which incorporates this phenomenon. Wang and Qi. 1980. Ming. et al. et al. et al. 1990. b. indium or chromium. et al.. 1980.. in the process of crystal growth. et al. Y. Growth striation method has been used to grow LN. On the other hand.. et al. et al. 1998). et al. Magel. c. 1995). The presence of the internal field results in axial anisotropy of the coercive field. 1988a. When cooling through the Curie point. 1986. 1986.1 wt%—0. Ballman and Brown (1972) experimented with a pulsed field technique to invert single-domain LT crystals at different temperatures. 1992. b. For a plane electrode sample.. This may enable the fabrication of bulk devices (thickner than a few millimeters) with better mechanical stability and performance. Both types of domain structure show potential applications also in acoustic devices (Xu. to obtain uniform short-period domain structure essential for SHG of blue and UV light. LT. crystals with superlattice are formed automatically (Ming.. The modulated domain structure thus prepared is characterized by the fact that the direction of spontaneous polarization of domains is parallel to the domain boundaries.The applied electric field depends on temperature as well as on stoichiometry. If the electric pulse applied in the poling process is too long. et al. such as yttrium. 1982a. The total electric field is comprised of the sum of an applied external field. which can only be prepared by the growth striation technique (Feng. the nucleation first occurs under the periodic electrode. The periods of the superlattice may be adjusted by choosing 302 . et al. Wang and Qi. a depolarization field due to the unscreened portion of the polarization charge. the Czochralski method. the regular variation in dopant concentration of growing crystal. 1993. It was found that the field required decreased with increasing temperature. Batchko et al. It was found that the electric field for domain reversal in stoichiometric LN is about one fifth of that in the congruent LN (Gopalan. 1985. 1992. the inverted domain first randomly nucleates at the interface between wafer and electrodes and imperfections in the interior in the form of needles. leading to spontaneous backswitching upon abrupt removal of the external field. et al. LT with stoichiometric content.. for example. Zhu... Cheng. e. which results in the growth striations. Xu. Ba2NaNb5O15 and TGS (triglycine sulphate) periodic DSL single crystals (Feng. Whereas for LT. et al. Up to now. 1986. Recent progress in growth technique makes it possible to grow LN. domain reversal in both uniform-electrode and patterned-electrode ferroelectrics is driven by the total electric field.

suitable pulling rate and rotation frequency or by changing the period of the modulating electric current.1 wt% Fe) single domain crystal for holographic record.2 (a) Optical geometry for recording a 2-D refractive index grating into a Fe: LN single domain crystal.. 1998) and even polarized or unpolarized light microscopes (Gopalan. The nonuniform distribution of solute.. In this case. 303 . 1997). et al. The fact may be explained as follows.2(a). 2-D or 3-D DSL (or say. Experimental result shows that the direction of spontaneous polarization of ferroelectric domain is determined by the gradient of solute concentration in growth striations. b. Zheng. et al. which in a crystal is generally ionized.. 1996a. et al. other methods should be used.2(a). 19. 1998). S1.. One most commonly used to reveal the structure is to etch the sample. 1996a.. such as by volume holographic record and thermal fixation.2 Preparation of DSL by Using Photorefractive Effect Usually domain inversion does not change the dielectric constants of the material. is equivalent to the nonuniform space-charge distribution in the crystal and a nonuniform internal electric field is produced in it. Thus a 2-D square periodic grating can be recorded into the crystal as shown in Fig.2. scanning-tip microwave near-field microscopy (Lu. It can induce the metallic ions within the lattice to displace preferentially at a temperature close to the Curie point (Ming. et al.. we have used an oxidized Fe-doped LN (0. 1998). Wang. et al. 1-D. which are recombined and interfered to cause spatial variations of the refractive index. 1996) have been applied successfully to observe the domain structure nondestructively. energy dispersive X-ray analysis has been used to measure the solute fluctuation in growth striations. If a beam of an argon-ion laser is split into four equal-intensity ones and an S4 is applied parallel to the normal of the sheet of Fig. The oxidized Fe: LN sample exhibits high resistance to relax ation and the grating remains stable after the writing beams are removed. S2. photonic crystals) can be realized. Recently environment scanning electron microscopy (Zhu and Cao. et al. 19. In order to modulate the dielectric constants of a DSL. 19. and S3. In order to reveal the relationship between solute fluctuation and the ferroelectric domain structures. 1993a. a 3-D cubic DSL may be formed (Xu and Ming. Iin is the incident wave satisfying the exact Bragg condition of four-wave diffraction. In our experiments. (b) Schematic diagram of four-wave diffraction. 1982a). scanning force microscopy (Eng. et al. The domain structure can be observed using several methods. Figure 19. b). et al... A beam of the blue line of an argon-ion laser is split into three nearly-equal-intensity ones. coherent X-rays (Hu. Another advantage of the growth method is that it is easy to dope some active ions into the crystal during growth process for the design of multifunctional laser devices (Lu. 1997).

2. χij is linear susceptibility. In that case. z). The third-order term figures in such diverse phenomena as third-harmonic generation. self-focusing. The dijk coefficients are measured most often in SHG experiments. 1984) where Pi is the ith component of the spontaneous polarization (i = x.19. the dijk can be contracted as diJ with i = 1.and difference-frequency generation. y. ε0 is dielectric constant of vacuum.3 Outline of the Nonlinear Optics It is well known for intense fields that the induced polarization P of the material should be expressed as (Yariv and Yeh. El is electric fields (l = 1. for sum. respectively). optical phase conjugation and Kerr nonlinearity.3 and J = 1-6. The nonlinear optical response characterized by the parameter tensors dijk and χijkl gives rise to numerous interesting phenomena and applications. and for parametric amplification and oscillation. second harmonic and third harmonic. Thus we can quantify the SHG performance for a particular material or crystal orientation to obtain 304 . The second-order nonlinearity is responsible for second-harmonic generation. dijk is second-order nonlinear optical coefficients.2. Raman and Brillouin scattering.3 refer to fundamental. χijkl is third-order nonlinear optical susceptibility.

e is speed of light in vacuum. λ is wavelength of light.2.(19. since symmetry allows cancellation or equalization of certain coefficients. L is total length of the sample. deff is effective nonlinear coefficient. l is light intensity. 19.4 Wave Vector Conservation Usually wave vector conservation plays an important role in interactions between electromagnetic waves and media. a relation similar to Eq. then by using the Fourier transformation (Yariv and Yeh. respectively). π is modulation ratio of the two-dimensional nonlinear superlattice with π = nx/ny.where diJ are second-order nonlinear optical coefficients. If a modulated structure is introduced into the crystal.Gm (or Gm. One best known example is the Bragg condition in X-ray diffraction. where the wave vector conservation between the incident and diffracted X-rays is 305 . the matrix is reduced to The conversion efficiency of the SHG is given by where η is conversion efficiency.2k1. The only difference is that the phase mismatch Δk is changed into ΔK. 1984). For example. whether the interactions are linear or nonlinear. The matrix can usually be simplified. nl is the refractive indices (l = 1. Δk is wave vector mismatch in a homogeneous media with Δk = k2 . second harmonic and third harmonic. for LN.3 refer to fundamental.2k1 .n).4) can be obtained where ΔK is wave vector mismatch in a superlattice with ΔK = k2 . in which a reciprocal vector provided by the modulated structure is involved.

1989). In QPM scheme a periodicity is introduced into the nonlinear media. the wave vector conservation is just the so-called PM condition.2. where the two waves experience the same refractive indices. second harmonic and third harmonic. The QPM condition is given by 306 .In its most efficient form QPM is obtained when the sign of the nonlinear coefficient is reversed every coherence length. more than one Bragg condition. That is. whereas in a 2-D DSL the reciprocal vectors can be adjusted to make the incident waves satisfy the two conditions simultaneously. Clearly.3 refer to fundamental. In SHG process. In that case.(19. when where kl are wave vecitors (l = 1. the PM condition can be obtained from Eq. n2 = n1 and consequently propagate with the same phase velocity. Among the nonlinear interaction regime. 1962). the latter to the third-order nonlinear process.and difference-frequency generation. The former one is related to the second-order nonlinear process. energy will be transferred back and forth periodically with a coherence length where lc is coherence length. for example. the SH conversion efficiency grows quadratically along the propagation direction. In that case.fulfilled with a reciprocal vector provided by the crystal lattice. more interesting phenomena exist related to the wave vector conservation. the wave vector conservation involves light waves with different wavelengths. In the case of SHG. In the linear interaction regime. which can be a linear refractive index modulation or a modulation of the nonlinearity. The same concept can be extended to other nonlinear optical frequency conversion processes. the phase mismatch between the fundamental and the second harmonic can be compensated either using the birefringence of the crystal (birefringence PM method) or using the reciprocal vectors in a DSL (QPM method) (Armstrong. If the PM condition is violated (Δk ≠ 0) then the SH conversion efficiency will oscillate sinusoidally. In optical range.4). the most studied are optical frequency conversion and Kerr-form nonlinearity. In the optical frequency conversion process. This can be realized in birefringent crystals. such as the sum. two Bragg conditions can be fulfilled (Feng and Ming. et al. Bragg condition is important for constructive interference to take place. respectively). The treatment can be extended to light transmission in 2-D DSL. It is the reciprocal vectors provided by the modulated structure that is used to compensate for the phase mismatch. It is worth pointing out that an X-ray can hardly satisfy two Bragg conditions at the same time in a crystal because the lattice periods are nonadjustable. when the light transmission in a 1-D DSL is considered..

In 1-D DSLs. et al. 1991.(19. thus providing greater conversion efficiency. c. b.. b..3 depicts the relationship between the SHG and the length of the sample for the three different cases. Agranovich. Figure 19. 1993a. is determined by the value of a set of parameters which are defined as the RIM strengths of the 2-D periodic structure. 1986. The advantage of QPM over the birefringence PM is that it permits access to the highest effective nonlinear coefficients of the materials. Λ is period of the periodic superlattice. Winful. Figure 19. 1995. 1994. In 2-D DSLs. QPM with all waves polarized parallel to the z axis yields a gain enhancement over the birefringence phase-matched process of (2d33/πd31)2 ≈ 23. LT crystals). even interactions for which birefringence PM is impossible (for example. 1996a. Chen. 1993b. et al. the situation becomes quite different. the intensities of the multidiffracted waves are oscillation functions of these parameters.where Gm are reciprocal vectors of one-dimensional periodic superlattices. which is characteristically different from the phase-mismatch mechanism. et al. 1994. as can be seen in Eq. He and Cada. Another significant advantage of QPM is that any interaction within the transparency range of the material can be noncritically phase matched at any temperature. 307 . 1997.. when the transmitting light satisfies the exact Bragg condition of multiwave diffraction. whether the transmission state is located in the forbidden band or in the allowed band. The bistability in a 1-D DSL is thus attributed to the phase-mismatch mechanism. When optical bistability is discussed in 1-D and 2-D DSLs with Kerr-form nonlinearity. If the values of these parameters are arranged suitably.. It is the change of the phase mismatch between the propagating wave vector and the reciprocal vector provided by the periodic structure that brings the incident wave from a forbidden transmission state to an allowed state or from a low-transmission state to a high-transmission state (Xu and Ming. exists in a 2-D DSL containing Kerr-form nonlinearity. Recent research work by present authors (Xu and Ming. 1996a. Changes of these values will lead to high-or low-transmission states for each diffracted wave. the light will propagate in the allowed band. In LN. e. the light transmission in the exact phase-matched condition (the incident wave vector satisfies the exact Bragg condition) corresponds to the forbidden state. Delyon. b). 1991. has revealed that a novel bistable mechanism. the refractive index-modulation (RIM) mechanism. Wang. that is. since in the allowed band in the exact Bragg condition.3 The relationship between the SH intensity (relative value) and wave vector mismatch. 1979). d.. et al.5). et al.

. 1996.. Hadi. 1998).5 Nonlinear Optical Frequency Conversion in 1-D Periodic DSLs As early as 1980 (Feng. Eger. High-efficiency QPM SHG has been demonstrated in LN DSL and KTP DSL in both cw and pulsed regimes. et al. 1996a.. 1997. we verified the QPM theory proposed by Bloembergen et al. et al.6 92 96. Englander. Landry and Maldonado. b.75 2. The highest enhancement obtained is 16. Table 19. Reid. et al. Internal conversion efficiency of 64% was achieved using a KTP DSL for single-pass SHG of high-repetition-rate.6 16.4 4. b.. By placing a KTP DSL in an external resonant cavity. 1995. Arie. prepared through the application of an alternating electric current during the growth process.. 1997.340 0. 1994. et al. Serkland. 1991..8 0.. (1990) realized the blue light SHG in an LN fiber DSL. 1997. Ito. Arbore.. 1997a. 1998. 1997. respectively. et al. Webjorn. b. 1962).408 0.612 0. et al.. With these periodic DSLs. Arbore and Fejer. 1997) and 65% (Pruneri.. 1996.3 16. et al. d31) 29. compact disc players etc. 1980. Wang.. DSLs show 308 . et al.. Yamada. 1998. 1994a. Burr.680 In 1985.. 1998. Kintaka. 1998.476 0. et al. Miller.. et al. et al. 1998.. Later. When used for optical parametric oscillator (OPO)... et al.. b. et al. 1995. Zhu. 1997. single-pass cw and quasi-cw SHG with efficiencies high as 42% (Miller. et al. has made great progress (Feng.. et al. et al. et al. et al. et al. et al. d33) 1. Later with the same method. In 1990s.. 1997. Lu. in 1962 (Armstrong. et al.. 1997.1 The enhancement factors for DSL LN (QPM for d33 relative to the single domain crystal with PM for d31) SH intensity relative value (PM. 1992..5 3. Chen and Risk. et al. Feisst and Koidl (1985) performed the experiment with an LN DSL of less period.6 16. spurred by the need for blue light laser sources for data storage... et al.. Zheng. 1997. c. low-energy. Chou... 1998. 1997). Missey. Qin. Karlsson. et al..7 7 Enhancement factor 16. 1998. Kartaloglu. et al. Magel et al. d. 1996. 1980). et al.1 13.. Myers. close to the theoretical one. 1997. 1996) were realized in LN DSLs.1 shows the results. diode-pumped lasers (Englander. 1995a.. 1994. we fabricated the first periodic DSL LT (Wang. 1998... Reid.544 0..5 5. 23. 1997. Bierlein. et al. Mizuuchi and Yamamoto. et al. 1997.7 41 57 74.9. et al. Mizuuchi.19.. the QPM technique.9 16. et al. Table 19. 1986).. we prepared for the first time a periodic DSL LN by Czochralski method. 1990. et al.. 1994. 1997.8 Length of crystal (mm) 1 2 3 4 5 6 Number of domains 100 120 140 160 180 200 SH intensity relative value (QPM. et al. et al. For example. 1993. Gupta. 1998). 1998. et al. et al. conversion efficiency of 55% was obtained for a cw Nd:YAG laser (Arie. e.

advantages such as high gain. et al. et al.... and fs) has been obtained with periodic DSL LN. Missey. The conversion efficiency can be improved by confining the field to a waveguide.2 cm long first-order QPM-LN sample with a 64% quantum efficiency and a threshold less than 1 W. Reid. during the same period.. 1997. Mizuuchi and Yamamoto. low threshold and engineerability of domain structures.. 1997. et al. et al. et al. 1996a. respectively. Yi. Periodic DSL Nd: MgO: LN has been grown for self-frequency doubling (Lu.. et al. 1996d). 1992. by intracavity frequency doubling the outputs (signal and idler waves). 405 nm blue light and CW 1. c). 1997).2 Parameters of DSL LN samples and results of SHG experiments by using an OPO as a fundamental source Fundamental wavelength (µm) Efficiency (%) Sample No. et al.. Eger. Batchko et al. b. 1991. Thus far in our lab.35 mW. DSL LN (Burr. referr to the review article by Byer (1997).. 1997a... diode-pumped. The low coercive field of RTA. et al. 1998) with 1 mm thickness were fabricated successfully. thus making it possible to develop a robust. Serkland. (1998) demonstrated a 532 nm cw-pumped single-resonant OPO based on a 5. Zhu. 1996. SBN samples prepared by RTPT or Czochralski method (Feng. 1998. Table 19. dthick (mm) Period (µm) N (periods) 309 . Wang... 1998.. b). et al. et al. Lu. This inhibits the use of DSL LN and LT in UV SHG and high-power pulsed OPOs. Usually. et al. 1997. Kartaloglu. et al. and high resistance to photorefractive damage. et al..7 µm was prepared for UV SHG (Mizuuchi. 1997). 1986. 1980. e). et al.. Webjorn. Because of this. 1998). 1996. b. together with its high damage threshold. et al. 489 nm blue light generation by directly doubling an 810 nm GaAlAs laser diode and a 978 nm InGaAs laser diode. it is possible.. Arbore and Fejer. et al. 1996c.34 mW. b) and KTP (Wang. et al. 1996).. Continuous wave (CW) 0. et al. For more detailed discussions on the SHG and OPO with the DSL.. 1995a. waveguide DSLs have also attracted much attention (Lim. SBN (Zhu.. The guide wave interaction allows longer interaction distances at high field intensities by preventing diffraction beam spreading. For example. 1996a. miniaturized OPO (Myers. 1994a. which allows poling of thick crystals (3 mm) (Karlsson. 1997. Burr... Visible dual-wavelength light generation through upconversion and QPM frequency doubling has been realized in erbium-doped periodic DSL LN (Zheng. have been reported (Lu.. DSL LN and LT are limited to periods not very short and to thicknesses ≤1 mm because of the side growth of inverted domains.. 1989. to generate blue and red light for display applications. with the improvement of the poling technique and the use of new materials. et al. 1997).2 shows the results obtained for several samples by using a picosecond automatic tunable OPO as a fundamental source (Lu.. The single pass SH conversion efficiency in bulk nonlinear devices is limited by diffraction spreading of the focussed laser beam. et al. et al. 1992. High-quality DSL LT with period as short as 1. 1998). New ideas such as balanced phase-matching was proposed (Bierlein. low temperature dependence. 1990). 1989. efficient pulsed SHG (including ns. et al.. et al.. 1997a. this situation has been changed gradually. LT. 1997. Kintaka. High-efficiency QPM SHG was realized in waveguide DSLs (Mizuuchi and Yamamoto. makes this material more suitable for high-power applications. However. 1997). With all these achievements. et al. et al. Hadi. all solid-state. et al. ps. Table 19.

1997a.1 2 3 4 5 0. et al.980 1. it is of interest to be able to fabricate and study such superlattices.3 220 230 300 310 180 0. Superlattices with different quasiperiodic modulation have been predicted to exhibit different properties.0 17.50 2.4 5. 1990. Then a question may be raised: Can this kind of material be of any practical use? It is well known that the key to QPM is to construct a 1-D periodic structure that provides a reciprocal vector to compensate the mismatch of wave vectors due to dispersive effect of refractive index. not only the QPM multiwavelength SHG but also some coupled parametric processes. Compared with the periodic structure. such as the third-harmonic generation (THG) and fourth-harmonic generation.20 1. This fact makes the QPDSL more flexible in structure designing. Therefore.6 Nonlinear Optical Frequency Conversion in 1-D QPDSLs Before 1984. 1992). b.2 24. 1990. Janot.815 0.2 6.78 1. 310 .026 1.4 8. This is an example of possible applications of quasiperiodic structure materials in nonlinear optics. Because of this. In other words.8 3.. 1997. The most famous ones are those with Fibonacci sequence and its generalizations.6. but its symmetry is higher than that of an aperiodic structure. et al. Zhu.62 0.. Qin. a QPDSL can provide more reciprocal vectors to the QPM optical parametric process. The discovery of quasicrystal has opened up a new field in condensed matter physics and therefore attracted much attention (Steinhardt and Ostlund.56 2.1 The Construction of QPDSL There are several types of quasiperiodic structures. research work on superlattices was mainly focused on periodic structures. et al. can be realized with high efficiency (Feng. 1999). 1990). which can be generated by the concurrent inflation rule: A → Ap B and B → A (where p is positive integer) (Birch.0 4.860 0.8 19.130 3.. 1998. Its reciprocal vectors are governed by two integers and two structural parameters rather than by one integer and one structural parameter as in the case of the periodic one.. et al.0 19. 19. a 1-D quasiperiodic dielectric superlattice (QPDSL) has a low space group symmetry. Therefore. the reciprocal vectors of a periodic DSL are determined by an integer and one structural parameter. This 1-D periodic structure can provide a series of reciprocal vectors. each of which is an integer times a primitive vector.

When p = 1. each block is composed of a pair of oppositely polarized domains. 19. lA1 = lB1 = l. Here.. In our case. (b) Schematic diagram of a QPDSL with Fibonacci sequence. respectively.4 shows an example of QPDSL with p = 1.1) st generation followed by the (j . 1999).2 Theoretical Treatment of the Nonlinear Optical Processes in QPDSLs 311 . lA1 is chosen to be equal to lB1.6. The thickness of the positive ferroelectric domain in blocks A and B are lA1 and lB1. The arrangement of the two types of block follow the generalized Fibonacci sequence: where (pSj-1) Sj-2 means a sequence of p (j . et al. (a) Two building blocks: A and B. that is.A typical generalized Fibonacci ferroelectric QPDSL is constructed from two building blocks A and B (Qin. The thickness of the negative ferroelectric domain in block A is lA2 and that in block B is lB2.4 A QPDSL made from a LT single crystal. Figure 19. Figure 19. each composed of one positive and one negative ferroelectric domain. the sequence is just the Fibonacci sequence.2) nd generation.

and E3 must be taken into account. P = ∑l = 1. ε is dielectric constant. LN. 1990) 312 . we consider a case in which a single laser beam with ω1 = ω is incident from the left onto the surface of a QPDSL made from.Here. Here these three electric fields. 3 Pl. 2.4. PNL: nonlinear polarization. The parametric SHG and THG processes can be analyzed by solving the coupled nonlinear wave equations that describe the interaction of the three fields in the 1-D QPDSL structure: where Al 2 is proportional to the photon flux at ωl with function with I = 1. the SHG and THG exist simultaneously in the QPDSL. PL: linear polarization. E1. 19. 2. propagates along the x axis with its polarization along the z axis in order to use the largest nonlinear optical coefficient d33 as shown in Fig. E2.. for example. et al. P = PL + PNL. which satisfy the wave equation: where E = ∑l = 1. and 3 f (x) is a quasiperiodic Here f (x) can be Fourier transformed to (Birch. µ0 is the magnetic permeability of vacuum. Through the nonlinear optical effect. 3 El. 2.

. (19. and Here m and n are two integers and D = γ(p)IA+IB. In fact.e. the p th "precious mean". the coupled Eqs.with the reciprocal vector of one-dimensional quasiperiodic superlattices where with p an integer. 313 .14) can be solved analytically for the boundary conditions of A2(0) = 0 and A3(0) = 0 under a small signal approximation. i. If the non-phase-matched components are ignored. only the Fourier component that is phase-matched contributes significantly to the parametric interaction.10) become: with Equation (19.

1984): 314 .with Under QPM conditions: Equation (19.15) can be simplified to Using the following relation. we can get the harmonic intensity (Shen.

the situation becomes much more complex.14). then we can get the conversion efficiency (Zhu.3 The Effective Nonlinear Optical Coefficients For QPM SHG in a periodic DSL.6. the second harmonic generated through the second-order nonlinear process and the third harmonic generated through the third-order nonlinear process are proportional to L2 (Armstrong. Here because of the coupling effect between the SHG and sum-frequency generation processes. (19. the conversion efficiency is proportional to the square of the effective nonlinear optical coefficient.. 1997a): Usually under the small signal approximation. Thus it is helpful to derive the expression for the effective nonlinear optical coefficients. the second-harmonic spectrum can be obtained and the peak positions of the SHG are determined by ΔK1 = 0. Thus it is possible to obtain THG in a QPDSL with high efficiency. the modulated nonlinear coefficient d(x) = d33f(x). For the QPDSL. the QPM condition Eq. it can be seen clearly that the effective nonlinear optical coefficients play an important role in nonlinear parametric processes. if we let A3 = 0 and under the small signal approximation. In order to see the relationship.If k2A1L is very small. et al.16). n = 1 corresponds to the first-order QPM with the largest conversion efficiency. In addition. According to Eq. et al. the effective nonlinear coefficient is 315 . 19. For QPM THG in a QPDSL. we can get: From this result.. 1992). it is needed to obtain the expression of the effective nonlinear optical coefficient for QPDSL. the third harmonic generated through the second-order nonlinear process is proportional to L4. (19. 1962).13). (19.. et al. From Eq. which is represented by with I the length of the reverse domain (Fejer.

The SHG spectrum of the QPDSL LT was measured with the fundamental tuned in the infrared.2830 1.n = πD-1(1+γ(p))(mIA-nIB).6825 0. As has been pointed out that here the QPM multiwavelength SHGs are wholly determined by the distribution of the reciprocal vectors of the QPDSL. et al. With the QPDSL samples. 1999) To verify the theoretical predictions.4) (2. et al.3 shows the results for m = 1. Table 19. green. Therefore with the aid of Fourier transformation. Qin.. n (3.3650 1.6417 0.1) Fundamental wavelength (µm) Cal.7845 Reciprocal vectors Gm. et al.where Xm. However. the value of dm..3 Experimental results of SHG spectrum in the QPDSL LT Harmonic wavelength (µm) meas.6.3640 1. we obtained QPM second harmonic blue. 1990.1) (1. the effective nonlinear coefficient for the periodic DSL. The measured and calculated results are in good agreement. the so-called Fibonacci type and the other one a generalized QPDSL with p = 2. (19.3) (1.2834 1. When IA/IB.5 9. 1999). 0. 0. such as I and the ratio IA/IB. 1995).1 2. in the SHG spectra of the QPDSL. Note that when p = 1. et al. 1997b.4 It is theoretically predicted and experimentally observed that the X-ray diffraction and Raman spectra of quasiperiodic superlattice exhibit self-similarity.5687 Input energy Output energy FWHM (nm) Efficiency (%) (µJ) 40 40 33 30 54 meas. 316 . by careful analysis to the measured spectrum.9726 1.. the result is just the one for Fibonacci sequence.5699 (µJ) 3 7 3 2 11 0.85 1.0820 1. 19. This is due to the dispersive effect of the refractive index.7 20.4 0..2) (2.0846 1. red and infrared light output with conversion efficiencies up to about 5%—20%. Obviously.9720 1. The sample was fabricated by poling a z-cut LT single domain wafer at room temperature (Zhu. the self-similarity no longer holds. the QPDSL turns back to a periodic DSL and Eq.4 QPM Multiwavelength SHG (Zhu.n depends strongly on the adjustable structure parameters.5423 0.5 7.1 6. arbitrary wavelength-response functions can be obtained by design of appropriate DSL (Chou. two types of QPDSL have been fabricated: one with p = 1. 0. although the reciprocal vector does in reciprocal space.4863 0.21) reduces to with m = n.5 17. Table 19.3 0.

Qin.. Several THGs have been detected. However. Wang. The creation of the third harmonic directly from a third-order nonlinear process is of little practical importance because of the intrinsic low third-order optical nonlinearity. The study can be divided into two classes: linear regime and nonlinear regime. strong localization of light (John. 1998. Recently. 19. 1993a.5 Direct THG (Feng. et al. 1990). However. 1996a. 1997a. With the aid of RTPT. For the QPDSL. et al.16). Qin. QPM THG has been demonstrated using a simple silica structure of six modulation periods through cubic nonlinearity (χijkl) (Williams.7 Optical Bistability in a 2-D DSL Optical wave propagation in a dielectric structure with spatially periodic refractive index has been a topic for a long time. et al. et al. we have performed a systematic study on QPDSL SBN related to SHG and THG (Zhu. 1984). the dispersion relationship of the refractive index has been deduced (Zhu. b. 1990.QPM structures with multiple phase-matching wavelengths can be used for wavelength-division-multiplexed wavelength conversion. Using the SH spectra obtained in QPDSL either with p = 1 or p = 2. Zhu. et al.. He and Cada. et 317 . 1997). et al. 1997). the QPM conditions for THG in a collinear interaction are given by Eq. However. In this regard. 1999). can occur in these materials. 1987). 19. et al. an efficient third harmonic can be generated only when both the SHG and SFG processes are quasiphase matched.. e. only one TH has a high conversion efficiency (>20%).. physical phenomena including inhibition of spontaneous emission and energy transfer (Yablonovitch. b. and photon-atom bound states (John and Wang. c.. Theoretical analysis has been shown that the THG can be generated through the nearly QPM SFG with the SHG either quasiphase matched or mismatched.. In linear regime in which the dielectric constant is independent of the optical field intensity. et al. (19.. et al..6. et al. 1997b. Others are very weak. 1998). et al. 1986. Winful. 1997a. 1991. 1998).. In an LN waveguide. 1994. Agranovich. Conventionally. if nonlinearity is introduced into the structure. 1991. b. These materials are known as photonic band gap materials or photonic crystals. an efficient THG was achieved by a two-step process. Two nonlinear optical crystals are needed: the first one for SHG and the second one for sum-frequency generation (Shen. ultraviolet THG of 355 nm has been observed (Kintaka. THG was tested with a tunable optical parametric oscillator.. Continuous-wave frequency tripling by simultaneous three-wave mixings has been realized in a periodically poled LiNbO3 (LN) crystal (Pfister. d. 1999) THG has a wide application as a means to extend coherent light sources to short wavelengths. novel phenomena such as optical bistability (Xu and Ming. Delyon. Here only one crystal is needed and the harmonic generation can be realized using the largest nonlinear optical coefficient over the entire transparency range of the material with high efficiency... QPDSL has some advantages over the conventional method. 1987). et al.

1988.. b. 1993a. Thus the refractive index of a 2-D nonlinear DSL is given by Figure 19. Mills and Trullingre. He and Cada 1991). 1996b). 1996a.. d. the related parameter is the mismatch of the propagating wave vector that detunes from the cavity-matching condition or the Bragg condition. et al.. treated the case of two incident waves (Chen. 1995). 19. d. Usually for optical bistability to take place in a medium. b. et al. (b) Bragg condition with four reciprocal points located on the Ewald sphere.7. (Wang. these materials may be termed nonlinear photonic crystals. 1994) showed that a 2-D DSL can exhibit optical multistability and instability under exact Bragg conditions. 1996b). 1997. Compared with the phase-mismatched mechanism. (a) Schematic of four-wave diffraction in real space. The dotted lines denote the incident-dependent RIM along the x direction formed by incident fields Ein1 and Ein2. et al.. Wang. Winful. As such. 1976) or in a 1-D superlattice (Agranovich. Chen et al. requiring that the values of these parameters change with the transmission field. (Xu and Ming. 1997. This kind of bistability is thus attributed to the phase-mismatched mechanism.. 19. 1979. sinusoidally modulated in the x and y directions. Wang.5 Four-wave diffraction in a 2-D DSL. et al. theoretical and experimental work has revealed a novel bistable mechanism. Wang et al. gap solitary waves (Chen and Mills. 1995. Taking nonlinearity of the medium into account. e. We assume that the linear refractive index of a 2-D nonlinear DSL is weakly. Light propagation in a 2-D DSL in which the refractive index is sinusoidally modulated in two dimensions was studied by Feng et al. 1993a. d. 1994..1 Bloch Wave Approach (Xu and Ming. The average energy density of the transmission field in the cavity or in the superlattice is an oscillation function of the parameter (Agranovich. 1994) will emerge. 1994. c. 1996c) We consider a lossless 2-D DSL with a simple Kerr-form nonlinearity shown in Fig. 318 . et al. 1996a. b.al. requiring that the transmission light field respond in nonlinear form to parameters that are related to the transmission process.. This nonlinear response element. 1995. 1997) discussed the influence of the modification of RIM strengths and the effect of non-Bragg incidence on the optical response in these structures. 1979). b). but the RIM strength of the 2-D DSL.. Chen. b.. However. two necessary elements are expected to coexist: one is the nonlinear response element. Delyon. 1991.e. He and Cada. c. 1991. 1993b. b. Chen. e. Xu et al. 1996a. Chen.5(a). 1994. Wang. the other is the positive feedback element. 1991. et al. 1987. and ultrashort pulse propagation (Scalora. b. in a 2-D DSL containing Kerr-form nonlinearity. et al.. e.. In common dispersive bistability in a Fabry-Perot etalon (Gibbs. Sterke and Sipe. 1986. et al. 1995. Some preliminary work concerning the 2-D DSL has been done by our group since 1989 (Xu and Ming. 1989). coupled with the feedback element that the wave vector's mismatch is established by the field's average energy density in the medium via the Kerr-form nonlinearity will produce bistability in the system's input/output relation. i. 1993a... self-induced transparency (Kozhekin and Kurizki. et al. et al. c. (Feng and Ming.. the RIM mechanism (Xu and Ming. et al. et al. et al. 1996a. et al. 1987.. 1995. 1989). 1996b). the related parameter in the RIM mechanism is not the wave vector's mismatch.

Here n0 is the average refractive index. 19. There are two wave vector conservation relations: From the above equations. 319 . According to the above discussions. four diffracted waves can be excited as indicated in Fig. taken to be rather weak. Gy are reciprocal vectors of two-dimensional superlattices. 1987). Another such structure would be a doubly periodic planar waveguide where Eq.h. two Bragg conditions can be expressed as: where kB is the Bragg wave vector and θB is the Bragg angle.5(a). for an incoming wave with wave vector k polarized in the z direction in the vicinity of Bragg incidence the Bloch waves in a 2-D nonlinear DSL can be decomposed into four partial modes.22) describes the distribution of an effective mode index (Zengerle. when an incoming wave Ein1 satisfies two Bragg conditions simultaneously. 19. respectively. within which multiwave dynamical diffraction may occur. nx. At a specified frequency of incoming wave.22) can be fabricated by using a holographic recording technique (Xu and Ming. ny are refractive index modulation along the x and y directions of two-dimensional superlattices.o and K. (19. In reciprocal space. nα is the Kerr coefficient. For a 2-D DSL. The 2-D DSL described by Eq. the wave vectors of the four waves are Ko. Gx. (19. the Bragg conditions set an angular range near the Bragg angle. Kh. 1993a). K.5(b). these four wave vectors are on the Ewald sphere as shown in Fig.

ξh) which are defined through (Feng and Ming.K2o/k2 ≈ . and 1 .where Eσ: electric fields in two-dimensional superlattices (σ = o. 19.27). which follow from inequalities nx no. (19. 1 . . 1989) 320 . The relation between ξo and ξh can be expressed as. These equations constitute the basis of our numerical calculations and discussions of the remaining parts of this paper. we obtain a nonlinear matrix equation for Eσ.K2-h/k2 ≈ 2ξh were used.2 Four-Path Switch: Linear Case (Feng and Ming. 1 .h indicate the different directions). Since the nonlinear response element of a medium can be found by checking the dynamics of light transmission in the corresponding linear dielectric system. we shall at first present some main results obtained in linear regime. the approximations 1 . We will discuss them in detail in the following sections. in the vicinity of Bragg incidence. (19.27) are expressed as where Mα = 2nα/no.2ξo.K2h/k2 ≈ . 1989) with k = k . Then carrying manipulations similar to the ones used in the linear multiwave diffraction dynamics.o. . To obtain Eq.K2-o/k2 ≈ 2ξo. h.7. The field-dependent RIM strengths in Eq. A useful representation of the dispersion effect caused by multiwave interaction in a 2-D nonlinear DSL is to introduce a new set of axes (ξo. and ny no.2ξh.

.29).5(a)) by appropriately modulating the value of =. 1994. (19.27).If the intensity of the incident optical wave is very weak. Wang. (19. When the incident wave satisfying the Bragg condition excites four diffracted waves. the refractive index of the 2-D DSL will be modulated by the optical waves through the terms ΔMβ in Eq. This phenomenon can be used to fabricate a four-path switch in which the modulation can be realized by applying two acoustic waves along two orthogonal directions. although there are four diffracted beams. (19.26) and (19. (19. (19.31) yields complex ξh values. = is modulation ratio of the two-dimensional nonlinear superlattice with = = nx/ny. According to Eqs. the incident beam can be diffracted into one of the four propagating directions (Fig.27) equal zero. It is expected that if a Kerr-form nonlinearity is considered. Thus it is to be expected that the bistability may be exhibited in the incident-diffracted relations of a 2-D DSL containing Kerr-form nonlinearity. the medium is a linear medium. b. this leads to complex Ko and Kh values. or the forbidden band. (19. =. When =>1.y. Numerical calculation shows that all four diffracted intensities are oscillation functions of the RIM strengths when =>1. e.3 A New Type of Optical Bistability Mechanism: Nonlinear Case with One Incident Wave (Xu and Ming. real ξh values are always obtained from Eq. c. 19. the values of the RIM strengths will be perturbed by the interference of the four diffracted waves in the transmission field. (19. for =>1 we obtain propagating Bloch wave and in this case the intensities of the four diffracted waves of a 2-D DSL are oscillation functions of RIM strengths.7. Eq. 0) in Eq. b. we have applied a kind of self-consistent method to achieve the incident-diffracted relations. the interference of the field will give perturbations to the values of the RIM strengths 321 . For =<1 and ρ in the range ρsin2θB <1/2My (1 . In this way. 1997) As the input power is increased. et al. 19. In other words. That is. This is the feedback element.27) to zero gives a dispersion relation: The solution for ξh is readily obtained: where ρ is angular deviation of the incoming light from the Bragg angle. x + y. To investigate possible bistability of the RIM mechanism. The related parameters here are the RIM strengths. 1996a. x . d.22) should be taken into account. The strength ratio can be obtained by controlling the intensity ratio of two acoustic waves. all the ΔMβ's (β = x. That is. (19. then the fourth term in Eq. In other words. the Kerr-form nonlinearity in Eq. y. Setting the determinant of matrix Eq. In this way. 1993a.22) can be neglected. their strengths can be adjusted by modulating the modulation ratio of the 2-D DSL. corresponding to evanescent Bloch waves. Such a dynamical behavior revealed in a 2-D DSL provides a new type of nonlinear response element.31) for all ρ.=2)1/2.

This RIM mechanism for bistability is characteristic of multiwave diffraction cases in 2-D DSL. the two are in a self-consistent manner.7 is one of the results recorded in the experiment.6 is one of our results that shows the intensities of four diffracted waves as functions of the incident intensity Iin. a Fe-doped LiNbO3 single crystal. Eventually this dynamical interaction between the transmission field and the RIM strengths will reach a stable state.e. et al. Figure 19.6 Relative intensities of four diffracted waves as functions of the incident intensity Iin (calculated). 1996b)... The hysteresis loop width depends on Mx and My. i.2(b) is a schematic of four-wave diffraction. It is not exhibited in a 1-D superlattice because there is only one parameter of RIM strength in a 1-D superlattice. Bistable 322 . The threshold for bistability here is comparable with that of the dispersive bistability in a Fabry-Perot etalon. The nonlinearity induced in this 2-D DSL can be proved to be in a form similar to the Kerr-type (Wang. There always appear discontinuous jumps of intensity in the bistable region and the jumps can be either from higher values to the lower or from the lower to the higher. Such a stable convergent self-consistent solution can be easily obtained with numerical computation. when the incident wave satisfies the Bragg condition. Figure 19. Thus a hysteresis loop is traced out. the transmissivity is a monotonous function of the parameter. The perturbed RIM strengths will then return to affect the transmission field.via the Kerr-form nonlinear term. The experiment was performed in a 2-D nonlinear DSL constructed by recording a 2-D refractive index grating into a photorefractive material. Figure 19. Figure 19. The shapes of the incident-diffracted curves are determined by the RIM strengths.

Because there is an interference field existing in the medium due to the incident wave diffracted into four directions. a hysteresis loop. In addition. The strengths of the perturbation depend on the incident intensity and they may be positive or negative. et al. The change of the values of the perturbed RIM strengths causes a change of the transmission-diffraction field. that is. By the electric field induced modulations on the refractive index. Figure 19. The arrows indicate where the switching occurs. with different interference field.. this system can enter the regions of bistability. the space charge pattern that the drifting of the free carriers is constructing coincides with the original one. and this changed field will return to affect the perturbations of the RIM strengths. and because of the low illuminating intensity and the low erase sensitivity in this oxidized sample (Orlowski.behavior with discontinuous jumps of the diffracted intensities. 1997). The occurrence of bistable behavior can be understood by the following analysis.7 Intensities of diffracted waves recorded as functions of the incident intensity Iin. which is expected to exist in such a 2-D DSL. In the illumination of the incident wave. the trapped electrons in the space charge pattern of the original grating are excited and drift. This fact provides the feedback element for the RIM mechanism. this redistribution of the trapped electrons relative to the former actually gives perturbations to the values of the original RIM strengths of the superlattice. respectively. 1993a). can be seen clearly and the jumps occur simultaneously for four diffracted waves. Diffracted intensities will thus change nonlinearly with the incident intensity. instability or chaos by means of either adjusting the incident intensity or changing the values of the RIM strengths (Xu and Ming. 323 .

optical bistability may disappear if the angular deviation is too large. We see that. and ρc = 0. Moreover. the results under Bragg incidence are also shown. ρ = 0. No optical switching exists when ρ>ρc. ρ = 0.8 shows the calculated results under four different angles of incidence. Optical bistability disappears as the deviation increases. 19. In the figure.755 mrad in (d).When the incident wave deviates from the Bragg condition.8 Influence of the angle of incidence on the optical response (calculated). 324 . then something new appears. The angular deviation is ρ = 0 in (a). in Fig. Figure 19. a non-Bragg incidence leads to a large increase in the threshold for optical bistability.29 mrad in (b). we only plot the intensity of one excited wave versus incoming intensity to illustrate the effect of non-Bragg incidence.8.58 mrad in (c). For comparison. Figure 19.

as shown in Fig. the nonlinear response in the medium leads to the formation of incident-dependent periodic RIM along the x direction with its periodicity characterized by Gx in reciprocal space and with its strength proportional to the incident intensities. This requires a nearly Bragg incidence.. the dotted lines denote the 325 . When Kerr-form nonlinearity is considered. 1996a). The interference formed by two incident waves in the medium is characterized by a periodic spatial variation of the intensity. (1995) considered the case of two incident waves.5(a)). In the figure. The above work can be extended to a heterosuperlattice-junction structure (Chen. In that case. two coherent incident waves Ein1 and Ein2. et al. 19. Optical limiting has been predicted theoretically in such a structure. 19. 1995. with the same incident Bragg angle. a simultaneous excitation of four diffracted waves is responsible for the existence of RIM optical bistability mechanism. 19. symmetrically fall down the 2-D DSL (see Fig.5(a). In a 2-D nonlinear DSL. et al. Chen et al.7. The limit in the angular deviation at which the system exhibits simple switching is characterized by a threshold that is called ρc.. 1996b) The above discussion involves only one incident wave.4 A New Type of Optical Bistability Mechanism: Nonlinear Case with Two Incident Waves (Chen.The physical reason for the occurrence of the above phenomenon is that under non-Bragg incidence the coupling of four diffracted waves in the structure is much reduced.

5(a) are overlapped). such as poled-polymer and fused-silica films. diffusion-bonded stacks of plates. 1998).incident-dependent RIM along the x direction. et al. Spatial switching between different output soliton state has been predicted in QPM geometries with dislocations. Such a transition only requires a very low input power. Qin. Thus optical bistability occurs. and straightforward integrability.8 Outlook Superlattices has opened an area to the development of new synthetic materials that do not exist in nature. et al. et al. 1999). When the incident-dependent periodic RIM matches the preconstructed RIM (namely the dotted and the solid lines in Fig. and thus the effective π. 1997. 326 . 1999). 1997). QPM also opens the search for better nonlinear media to new classes of materials. silica and other glasses are particularly attractive. 1998).. the inversion symmetry of the glass matrix prevents frequency conversion of coherent radiation through second-order parametric processes. Reid. a bit of enhancement of RIM strength along the x direction can lead to this kind of transition. such as erbium-doped fiber amplifiers and high-power cw and pulsed fiber lasers. much interest has been aroused on new applications of DSLs. Periodically poled glass waveguides and fibers are ideal for a wide range of QPM processes. Therefore. 19.. et al. et al. 19. moreover.. This kind of process is similar to that of volume grating formation. the two intense waves can bring their transmission from a forbidden transmission state into an allowed transmission state. The recent discovery that poling techniques can provide a permanent and large second-order nonlinearity in silica made it possible to implement QPM in glass and glass waveguides and fibers. With two incident waves. Unfortunately. is enhanced in proportion to the incident intensities.. Engineered QPM patterns also hold great promise for use in soliton systems. Among them. soliton-based signal compression and shaping in QPM structures with longitudinal chirps has been proposed (Torner. tilts and wells (Clausen. 1997.. For a 2-D DSL whose values of π is near but smaller than 1. 1998).. in the case of two incident waves. low cost. The flexibility in the choice of superlattice materials allows superlattices to exhibit a wide range of tailorable properties that are of interest for scientific and device purposes. etc. et al. for a 2-D DSL with its π less than 1. That is to say. rare-earth doping of glass fibers has allowed the development of important laser devices. et al. the total RIM strength along the x direction.. For example... a sufficient increase of the two incident intensities will lead to the values of effective π greater than 1. laterally patterned semiconductors and asymmetric quantum wells (Byer. such as frequency conversion of fiber lasers. a high optical damage threshold. such as engineerable compression of ultrashort pulses in chirped-periodic DSL (Arbore. quadratic spatial solitons has been observed in a DSL LN (Bourliaguet. which might be beneficial for constructing low power cost 2-D optical bistable devices. These glasses offer high transparency. amplitude squeezing (Serkland. 1997). 1998) and cascaded nonlinearity (Landry and Maldonado. More recently. Recently. wavelength division multiplexing (WDM) (Chou. et al. optical bistability with very low threshold can also occur when the relative phase between the two waves varies slowly within one cycle. since they are dominant materials in information technology and in the development of fiber laser sources.

A. Rarity. Erman. 22. V.. H. G. 24. B.. A. P. Opt. H. G. From the similarity between the real ionic crystal and the DSL. 151 (1997) Arbore M.. Appl. T. For example.. The ability to photolithgraphically pattern the DSL structure allows the consideration of prism and lens arrays for these applications.. Chang.. 2356 (1999) Bourliaguet B. Fejer R. References Agranovich V. other long wavelength optical properties. Katz and D. A. et al.. Apart from all of these. Arbore and M. Beam deflection with prism arrays and focal length control. Growth. J. generation of correlated photon pairs by parametric processes for quantum cryptography. R. 22. G.. 115.. de Angelis. M. Fejer. Galvanauskas. D.. Eger. 56.. C. G. et al. Laubacher J.. 75. M. Lett. Infrared absorption and polariton excitation in the DSL has been verified by experiments. L. we established one-to-one correspondence between the real ionic crystal and the DSL when piezoelectric coefficient modulation is taken into consideration. Tapster and J. Radnoczi. The DSL can also be applied to beam control. V. Nonlinear Opt. D. J.. Wahlstrom. Smith. L.. Ducuing and P.. Recently. 234 (1994) Byer R. 6. Ferroelectrics 4. Recently. Rosenman. Harter. such as the Raman scattering and Brillouin scattering might also be expected. C. infrared absorption and polariton excitation is resulted from the coupling between lattice vibrations and electromagnetic waves in an ionic crystal. Lett. 1996. R. Kiselev. D.. Chou and M. Nonlinear Optical Physics & Materials. M. V. L. L. whereas it might appear in the GHz region for a DSL. R. M. Couderc. D. 1458 (1997) Byer R. Phys.. B44. Skliar. R. Riklund and L.. Phys. 1341 (1997) Arie A. These results show that the possibilities for extending the use of DSL to control optical beams is open for further exploration and development. 1999). Yamada. S. The only different is they occur in different frequencies... even coupling effects between motion of electrons. Plettner. Bonfrate. Shur and L. Hanna and C. M... G. Severin. S. et al. B. M. R. D. 1996).. P. Weise. van der Poel. Lett. M. et al. A. Barthelemy. 7. U. Ross.. greater than 20%-efficient frequency doubling of 1532 nm nanosecond pulses has been realized in QPM germanosilicate optical fibers (Pruneri. Tang M. Miller. M. Opt. J. N.. Kazansky. 10917 (1991) Ando S. 10 398 (1990) Bonfrate G. beam focusing and beam steering (Chiu.... J. M. S. S. 1918 (1962) Ballman A. 1293 (1999) Batchko R. Phys. A. Bloembergen. Byer. Yamamoto. Lett. G. L. C.. et al.. Fejer. 1999). A. 168 (1998) Bierlein J. Brown. A. 549 (1997) 327 . R. 22. L. 127. photons and phonons can be expected to exist in the DSL structures. W. 1410 (1999) Burr K. 189 (1972) Batchko R. D. Y. M.. G. Phys. A. Lett. Fejer. Lett. Appl. et al. B41. Oron. D. Lett. Study on these effects is of fundamental interest in physics (Lu. G. M.. 23. Fejer. Woll. D. 69 (1991) Arbore M. Byer. Wallenberg.difference-frequency generation as a means for frequency conversion of telecommunication wavelengths. 1725 (1990) Birch J. T. P. Rev. and cascading of second-order nonlinearities to produce equivalent third-order effects (self-and cross-phase modulation) for all-optical switching (Pruneri. Korenfeld. 1999. Opt. Cryst. Opt. Wallenstein. 28 (1998) Armstrong J. Rev. Lett. M. Raman scattering appears in the THz region for a real ionic crystal. 24. Y. Fukui. Phys. A.. optical switching have been demonstrated successfully. Brown and C. Rev. Opt. Opt. 23. M. Pershan. Mills. G. For example. 1999). Opt. Lett. Pruneri.

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W. This is the result of ballistic conductance. de Heer. 1 The most likely application of carbon nanotubes in recent years is field emission. The conductance of a carbon nanotube was measured as a function of the depth with which the tube was inserted into a mercury bath (S. 2 Quantum conductance of nanowires is an important and interesting physics phenomenon. L.Appendix Figure IV. Figure IV. Z. several companies have demonstrated prototype displays using carbon nanotubes. Z. A. and Dr. Frank. L. A. Poncharal. P. Wang. It is necessary to point out that this phenomenon was observed only for carbon nanotubes that are structurally perfect and surface clean (Courtesy of Dr. In-situ TEM observation confirmed this phenomenon. Georgia Institute of Technology). Science 280 (1998) 1744). Shown in this figure is a dark-field TEM image displaying the field distribution at the tips of carbon nanotubes under an externally applied electric field (Courtesy of Dr. L. and it is usually observed in ultra-thin nanowires at low temperatures. Besides fundamentl studies. and W. Z. 332 . and it is believed to be a result of single graphite layer conductance due to the unique structure of graphite. No heat dissipation was observed in the nanotube. de Heer. Ruiping Gao and Dr. Wang. The most surprising fact is that a 20 nm diameter multi-walled carbon nanotube exhibts quantum conductance at room temperature. Georgia Institute of Technology). Wang.

Dai. the current flowing from the source to the drain is controlled. The substrate is silicon. By controlling the voltage applied between the backgate and the source. Science. The nanobelts are semiconductors and their conductance depends strongly on the molecules adsorbed on the surface. L. By carefully placing a single nanobelt into the gold electrodes and ensuring good contact between the nanobelt and the electrode. Pan. nano-size sensors using single nanobelts have been fabricated (Courtesy of M. L. Avouris. Field effect transistors (FETs) can be fabricated using individual nanobelts (Z. Dr. W. R. P. Shown here is an AFM image of the FET and its corresponding schematic diagram. Based on this principle. and Dr. Gold electrodes were built on the chip using lithographic technique. Wang). Wang. on which there is a thin layer of silica insulating that serves as the gate oxide. and Z. 291 (2001) 1947).Figure IV. Z. Z. 333 . 3 Nanobelts of semiconducting oxides are a group of materials for sensor and optoelectronic applications. Arnold. an FET is built.

This dynamic process has been recently studied for gold 334 . L. from metals and semiconductors to oxides and even to polymers. 5 It is Known that nanocrystals melt at a much lower temperature than the bulk. Figure IV. Shihe Yang and Dr. Wang).Figure IV. 4 A large group of materials have been found to form nanowires. This TEM image shows typical morphology of CuS material. which consists of long needles and short rods. Z. The needles have a diameter of 200 nm at their roots and 50 nm at tips. but how does the melting start? One may say it starts at the surface. Rods have a diameter about 200 nm (Courtesy of Dr.

. 104 (2000) 7867). and M. B. Phys. After being illuminated by nanosecond laser.. Xia et al. El-Sayed.nanorods using femto..and nano-second laser. Surface Sci. 440 (1999) L809). Nano Lett. b) TEM shows that point defects have been created inside the volume. 335 . (c) the nanorod has changed not only in its shape but also with a stacking fault.. It is clear that the melting starts simultaneously at the surface and inside the bulk (S. The formation of uniform silica shell involved the base-catalyzed hydrolysis of tetraethyl orthosilicate (TEOS) and subsequent condensation of silica on the silver surface (Courtesy of Dr. The silver nanowires were synthesized using a polyol method that involved the reduction of silver nitrate with ethylene glycol in the presence of poly(vinyl pyrrolidone). (a. Z. A. University of Washington. After being irradiated with femto-second laser. J. Y. Wang. Chem. Link. L. The as-synthesized nanorods are defect free (Wang et al. 6 TEM image of silver/silica coaxial nanocables synthesized by directly coating silver nanowires with amorphous silica. 2 (2002) 427). which is created to form the {111} surfaces. Figure IV.

and self-assembly is an important process for fabrication of photonic crystals. Mater. This figure shows an SEM image of an inverse opal fabricated by templating a sol-gel silicate precursor against opaline lattices of 380 nm polystyrene beads. University of Washington.Figure IV. This figure shows an SEM image of two linear chains self-assembled from 150 nm polystyrene beads by 336 . 12 (2001) 206). Adv. 8 Combining self-assembly with lithographic technique is an approach for future nanotechnology.. Figure IV. 7 Photonic crystals are meso-scale structures. Y.. The polymer beads have been selectively removed through etching with toluene (Courtesy of Dr. Xia et al.

dewetting of colloidal dispersions from a surface containing physical templates (a parallel array of trenches that were 150 and 150 nm in width and depth. Am. Y. The inset shows an SEM image of the templates that were fabricated using near field optical lithography with a binary phase shift mask (Courtesy of Dr. 337 ... respectively). Soc. Chem. Xia et al. 123 (2001) 8718). University of Washington. J.