臺灣博碩士論文加值系統

本文主要是利用金屬有機裂解法(Metal-Organic Decomposition, MOD)以旋鍍方式將多添加10 mol% PbO的Pb(Zr0.52Ti0.48)O3 (PZT)前置溶液鍍在Pt/Ti/SiO2/Si基板上，藉由近似爐管(conventional furnace)退火、連續式二氧化碳雷射(cw-CO2)退火及氟化氪準分子脈衝雷射(KrF excimer pulsed laser)退火三種不同的退火方式，將原本非晶相結構的薄膜成功轉變成具鈣鈦礦結構的薄膜。同時量測P-E曲線、介電常數性質，並藉由XRD、SEM、TEM等儀器觀察因不同退火製程對於薄膜在電性、結構及微觀上的差異性。
實驗結果顯示在電性方面，薄膜利用cw-CO2雷射進行退火，在能量為400 W(能量密度為127.3 W/cm2)持續15 s的條件下，測試電場為 450 kV/cm時，可以量測Pr值為12.4 μC/cm2約與近似爐管退火溫度 700℃持續5分鐘的12.9 μC/cm2相近，但Ec值為44.5 kV/cm卻小於爐管退火的103.3 kV/cm，將能量提高至450 W(能量密度為143.2 W/cm2)時，Pr值可高達25.2 μC/cm2，Ec值為50.0 kV/cm，比爐管退火優異許多。若利用KrF脈衝雷射進行退火，隨著能量增加，Pr值也隨之增加，能量為450 mJ(能量密度為1.3 GW/cm2)時，有最高之Pr值，但只有3.1 μC/cm2。
在結構方面，由XRD圖中可以觀察到利用爐管退火，其(100)晶面的相對強度遠高於其他晶面，且因昇溫速率較慢、持續時間過長使得薄膜直接由非晶相轉變成鈣鈦礦結構；若利用cw-CO2雷射退火試片，其(100)晶面的相對強度隨著功率及照射的時間增加而增加，且薄膜從原本的非晶相，先轉成焦綠石相，再形成鈣鈦礦結構。以SIMS觀察，薄膜經爐管退火後，表面鉛元素揮發嚴重，且內部元素相互擴散，若以cw-CO2退火，則此現象可加以改善。
在微觀方面，薄膜經爐管退火處理，在某些區域，因退火時間過短，晶粒成長較為細小，其繞射圖形為環狀圖形；而經KrF脈衝雷射退火之薄膜，有雙層不同結晶效應，上層之薄膜因吸收雷射光能促使晶粒成核成長，且因能量大使得晶粒較為粗大，由繞射圖形觀察其為點狀圖形，下層因為上層熱擴散而使薄膜結晶，但能量不足使得晶粒成長情況不佳，由繞射圖形觀察其為環狀圖形；而利用cw-CO2雷射退火之試片，發現薄膜之繞射圖形為點狀圖形，且沒有雙層結晶效應。
cw-CO2雷射可以在極短的時間內讓薄膜成核成長，對於擴散的抑制有極大的幫助，且在晶粒大小、粗糙度、電性方面皆比爐管退火好，可以提供另一種取代爐管退火的製程。對於KrF脈衝雷射而言，其因是能量皆被薄膜表面給吸收，對於厚膜退火而言並不是一項好的製程，其功能可能主要是幫助薄膜表面改質或對極薄的薄膜進行退火。

In this thesis, Pb(Zr0.52Ti0.48)O3 (PZT) precursors prepared by Metal-Organic Decomposition (MOD) were coated on the Pt (1500Å)/Ti (700 Å)/SiO2 (1500 Å)/Si (100 p-type) substrates. Additional PbO precursor (10 mol%) was added to the solution to compensate for the PbO losses occurring during the subsequent heat treatments of the PZT thin films. The structure of PZT thin films was transformed from the amorphous phase to the perovskite structure through treatments of furnace annealing (FA), cw-CO2 laser annealing (CLA) and KrF excimer pulsed laser annealing (ELA), respectively. Ferroelectric properties including P-E curve and dielectric constant were measured by commercial instruments. Macro- and micro-structures were investigated using x-ray diffractometry and electron microscopy.
The experimental results reveal that all films show the perovskite and polycrystalline structures using the above-mentioned three annealing methods. Ferroelectric properties show the remanent polarization (Pr) is 12.4 μC/cm2 using CLA with the power of 400 W (power density is 127.3 W/cm2) for 15 seconds. The value is closed to the process using the FA method with 700℃ for 5 minutes and 30 minutes. But the value of coercive electric field (Ec) using the CLA method which is smaller than that using the FA method is 44.5 kV/cm, If the power is raised to 450 W (power density is 143.2 W/cm2), Pr reaches 25.2 μC/cm2 and Ec is 50.0 kV/cm. If PZT thin films are annealed by the ELA method, the highest value of Pr is 3.1 μC/cm2 smaller than values using the FA and CLA methods.
Structural investigations show the relative intensity of the (100) plane higher than another planes ((110) and (111)) for specimens processed by the FA and CLA methods. Because of slow heating rate and long treating time, PZT thin films using a FA method transform from the amorphous to the perovskite phase directly. Contrast to PZT thin films using a CLA method transform from the amorphous phase to the pyrochlore structure before evolving to a perovskite phase. Secondary Ion Mass Spectroscopic (SIMS) investigations show that elements of PZT thin films evaporate and diffuse seriously in specimens using a FA method, and the phenomena can be improved greatly by a CLA method.
Microstructural results show that grains grow slowly in some regions using a FA method possessing low power density for annealing time 5 minutes. The grains whose the diffraction patterns exhibit ring patterns. If PZT thin films are annealed by ELA method, two layers of films crystallized differently are observed. As the upper film absorbs greater part photon energy, the large grains which revealed the spot reflections in diffraction patterns are observed. Because crystallization of the lower layer of the PZT film relies on the heat conduction from the upper layer, the value of the energy conducted is so poor that the grains are smaller, and therefore the ring diffraction patterns are exhibited. In contrast to the FA method, the CLA method provides suitable power density that is higher than FA method to anneal the films at an extremely short period of time and makes grains grow uniformly that diffraction patterns exhibit spot patterns. Comparing to the ELA method, the CLA method (λ=10.6 μm) posses longer wavelength than that (λ=248 nm) and can anneal complete PZT films (the thickness is approximately 0.2 μm), so that the method does not cause two layers of films crystallized differently.
In summary, the CLA method can make grains nucleate and grow within an extremely short period of time, and constrain effectively diffusion between films and the substrate. The grain size and ferroelectric properties using the CLA method are better than those using the FA method, and therefore the CLA appears to be an appropriate method to improve disadvantages of the FA. Whereas the KrF pulsed laser possessing short wavelength is suitable to improve the surface of thin films or anneal the extremely thin films.

第一章 前言................................................(1-1)
第二章 文獻回顧............................................(2-1)
2.1 鐵電材料之簡介....................................(2-1)
2.1.1 鐵電材料晶體結構定義........................(2-1)
2.1.2 鈣鈦礦結構..................................(2-2)
2.1.3 鐵電材料之特性..............................(2-4)
2.2 鈦鋯酸鉛鐵電材料之簡介............................(2-6)
2.2.1 鈦鋯酸鉛材料結構............................(2-6)
2.3 鐵電薄膜之製備....................................(2-9)
2.4 金屬有機裂解法之簡介.............................(2-10)
2.4.1 金屬有機裂解法之基本原理...................(2-10)
2.4.2 利用金屬有機裂解法合成鈦鋯酸鉛起始溶液.....(2-11)
2.4.3 金屬有機裂解法之鈦鋯酸鉛薄膜製備...........(2-13)
2.5 鐵電薄膜的應用與要求.............................(2-16)
2.6 雷射退火.........................................(2-18)
2.6.1 雷射退火簡介...............................(2-18)
2.6.2 雷射照射的吸收機...........................(2-23)
2.6.3 雷射退火處理的光源.........................(2-24)
2.6.3.1 脈衝雷射退火...........................(2-24)
2.6.3.2 連續波長雷射退火.......................(2-24)
2.6.4 熱傳導.....................................(2-25)
2.6.5 雷射退火晶粒成長機制.......................(2-26)
2.6.6 雷射製程參數對薄膜的影響...................(2-27)
第三章 實驗方法及步驟......................................(3-1)
3.1 實驗藥品規格及儀器總表............................(3-1)
3.2 鍍膜基板之製作....................................(3-3)
3.3 PZT前置溶液的製作.................................(3-3)
3.3.1 Lead 2-ethylhexanoate(Pb(C7H15COO)2)........(3-3)
3.3.2 Zirconium 2-ethylhexanoate(Zr((C7H15COO)4)..(3-4)
3.3.3 Titanium di-ethoxy-di-neodecanoate (Ti(OC2H5)2
(C9H19COO)2)................................(3-4)
3.3.4 Pb(Zr0.52Ti0.48)O3前置溶液之調配............(3-4)
3.4 薄膜的製備........................................(3-9)
3.4.1 基板的清潔..................................(3-9)
3.4.2 薄膜披覆...................................(3-10)
3.4.3 近似快速退火、二氧化碳雷射退火及KrF脈衝雷射退火
...........................................(3-10)
3.5 特性量測.........................................(3-11)
3.5.1 熱重分析儀.................................(3-11)
3.5.2 X-Ray 繞射分析儀...........................(3-11)
3.5.3 n & k薄膜測厚儀............................(3-11)
3.5.4 掃描式電子顯微鏡...........................(3-11)
3.5.5 穿透式電子顯微鏡...........................(3-12)
3.5.6 二次離子質譜儀.............................(3-12)
3.6 薄膜鐵電性質量測.................................(3-12)
3.6.1 上電極製作.................................(3-12)
3.6.2 極化-電場量測..............................(3-15)
3.6.3 介電常數量測...............................(3-15)
第四章 結果與討論..........................................(4-1)
4.1 金屬有機裂解法製備鈦鋯酸鉛之熱重分析..............(4-1)
4.2 金屬有機裂解法製備鈦鋯酸鉛粉末之X-Ray分析.........(4-3)
4.3 鈦鋯酸鉛薄膜之光性分析............................(4-5)
4.4 爐管退火製備鈦鋯酸鉛薄膜..........................(4-7)
4.4.1 X-Ray分析...................................(4-7)
4.4.2 電滯曲線...................................(4-12)
4.4.3 SEM分析....................................(4-14)
4.4.4 SIMS分析...................................(4-18)
4.4.5 TEM分析....................................(4-20)
4.5 氟化氪(KrF)脈衝雷射退火製備鈦鋯酸鉛薄膜..........(4-22)
4.5.1 X-Ray分析..................................(4-22)
4.5.2 電滯曲線...................................(4-24)
4.5.3 SEM分析....................................(4-25)
4.5.4 TEM分析....................................(4-26)
4.6 二氧化碳(CO2)雷射退火製備鈦鋯酸鉛薄膜............(4-29)
4.6.1 X-Ray分析..................................(4-29)
4.6.2 電滯曲線...................................(4-34)
4.6.3 SEM分析....................................(4-36)
4.6.4 SIMS分析...................................(4-40)
4.6.5 TEM分析....................................(4-42)
第五章 結論................................................(5-1)
參考文獻...................................................(6-1)

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