本論文主要在研究石英單晶在熔融氧化硼中的熱蝕，以及熱蝕對於相同結晶結構(phenakite structure)無機高分子正矽酸鋅與正矽酸鈹單晶的影響。石英單晶的(10 0)、(10 1)與(11 1)天然結晶面與(0001)拋光面，於500℃至700℃，經熔融氧化硼熱蝕後，藉由掃描式電子顯微鏡的觀察，熱蝕型態可區分為三種類型：單獨的差排蝕坑、排列有序的蝕坑與平底的蝕坑。石英單晶高溫的差排運動與蝕刻型態的發展，主要受到α-β位移式(displacive)相變化所引發的塑性和石英原有缺陷種類的影響。藉由這些觀察，熔融氧化硼確為研究石英動力學的極佳熱蝕液。至於正矽酸鹽(phenakite)的熱蝕研究包括三種：在1250℃循環式熱蝕、在700℃熔融氧化硼中熱蝕與室溫鹽酸以及氟酸水溶液的蝕刻。表面預熔、異向晶格蝕刻與缺陷蝕刻，對於正矽酸鋅的蝕刻有重要的影響。第一次熱循環可能引致雜質於差排露頭偏析，使得正矽酸鋅(0001)面上之六邊形差排蝕坑中央處有抗蝕丘產生。反射式紅外線光譜分析顯示，表面預熔物與正矽酸鋅有相同的結構單位，並循富矽之路徑可長成正矽酸鋅或富矽之化合物，表面之富矽化合物並可阻隔其晶面下的熱蝕。穿透式電子顯微鏡觀察證實，正矽酸鋅經過熱循環可產生明顯的多邊形化現象。石英與正矽酸鋅開裂與愈合的現象主要是受毛細作用力的影響。不論熱蝕或化學蝕刻，正矽酸鈹均比相同結晶結構的正矽酸鋅抗蝕，鈹與鋅在配位數4晶格位置能量(site energy)上的差異，對其蝕刻偏好應有重要的影響。

This thesis is about thermal etching of quartz single crystals with boron oxide melt and thermal etchings on inorganic polymeric single crystals of orthosilicates, willemite (Zn2SiO4) and phenakite (Be2SiO4), where isolated [SiO4] groups are polymerized by corner-sharing with other tetrahedral groups, such as [ZnO4] and [BeO4]. On the thermal etching of quartz, experiments were performed on quartz (10 0), (0001), (10 1) and (11 1) from 500℃ to 700℃. Three types of etch figures were recognized by scanning electron microscopy: isolated dislocation etch pit, aligned etch pits and flat etch pits. The effects of defect specification and α-β displacive phase transformation of quartz on its development of thermal etch figures were evaluated. By doing so, boron oxide melt was proved to be a useful etchant on the studies of defect types and dynamics of quartz. As for the thermal etching of phenakite type silicate, we conducted thermal-cycle etching of willemite at 1250℃, hydrochloric and hydrofluoric acid etchings of willemite and phenakite at room temperature, and boron oxide melt etching of willemite and phenakite at 700℃. Surface premelting, anisotropic lattice etching and defect etching were found to play important roles on the thermal etching of willemite. Impurity segregation at dislocation outcrops on willemite (0001) should occur in the first thermal cycling in order to nucleate hillocks at the centers of the hexagonal dislocation etch pits. Reflection IR spectroscopic analysis indicated the surface premelt has the same structural units as willemite, although the subsequent crystallization follows a silica rich path. A silica-rich surface coverage impedes the etching of crystal plane underneath. There is significant polygonization and cleaving-healing of willemite single crystal upon thermal cycling according to transmission electron microscopy observation. Phenakite has remarkable chemical and thermal etching resistance in comparison to its isostructure willemite due to site energy difference of Be and Zn in coordination number 4.

Contents
Page
Acknowledgement iv
Abstract v
Contents vii
List of tables ix
List of figures x

Chapter 1 Research outline and overview 1
Chapter 2 High temperature etching of single crystal quartz by boron oxide 4
2.1. Introduction 4
2.2. Experimental procedures 8
2.3 Results 10
2.3.1 Etch figures 10
2.3.1.1. Isolated etch pit 10
2.3.1.2. Aligned etch pits 11
2.3.1.3. Flat etch pit 13
2.3.1.4. Crack patterns 13
2.3.2. Raman spectroscopic analysis of borosilicate 13
2.4 Discussion 15
2.4.1. Original defects revealed by boron oxide melt etching 15
2.4.2. Defect configurations due to thermal cycling 16
2.4.3. Anisotropic lattice etching by borate 19
2.4.4. Role of boron oxide on etching 19
Chapter 3 High temperature etching of single crystal willemite 21
3.1. Introduction 21
3.2. Experimental procedures 24
3.3. Results 26
3.3.1. Thermal cycle 26
3.3.2. The chemical etching of willemite (0001) and phenakite
(0001) by boron oxide melt and hydrofluoric acid 28
3.3.3. The thermal etching and chemical etching of phenakite 28
3.3.4. Reflection IR spectroscopy analysis on willemite 28
3.3.5. TEM and electron channeling pattern analysis 29
3.4. Discussion 30
3.4.1. Surface melting and crystallization 30
3.4.2. Chemical etching resistance of willemite vs. phenakite 31
3.4.3. Formation of shallow hexagonal pit on willemite (0001) 32
3.4.4. Thermal cycling induced polygonization, cleaving and
healing of willemite 33
Chapter 4 Summary and remarks 34
References
Tables
Figures

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