2024年8月12日发(作者：盘以丹)
摘要
飛行時間式二次離子質譜術(ToF-SIMS)為一可分析固體表面化學資訊的技
術。其質量解析度可達10000，且靈敏度可達ppma至ppba等級。化學影像的橫
向解析度可藉由鎵離子槍而達到100nm。飛行時間式二次離子質譜術可應用在半
導體、微電子電路、奈米科技、高分子化學、生命科學、環境分析及藥物化學。
在第二章中，單根頭髮以縱向剖面的樣品準備形式進入ToF-SIMS分析。結
果看出外來物如染髮劑的分子離子的質譜訊號，且其離子影像分佈可看出染髮劑
已侵入至皮質層。
在第三章中，我們以飛行時間式二次離子質譜術分析含有8-羥基??鋁 (Alq3)
和NPB在氧化銦錫玻璃(ITO glass)的有機發光二極體元件。初期結果發現有經熱
處理之有機發光二極體元件會在NPB/ITO界面層產生一緩衝層。另外，NPB向
ITO擴散的情形也被觀察到。
在第四章中，二氧化矽(SiO2)和三氧化二鋁(Ai2O3)的全奈米粒子多層膜被
製造出來並由二次離子質譜術觀測其化學組成和成長機制，我們求出表面元素的
均勻度，並發現其長膜機制和分子模擬結果一致。
在第五章中，我們使用一特別的材料，二氧化鈦(TiO2)奈米粒子做為基層，
再反覆將二氧化矽和三氧化二鋁鍍在其上，再針對二氧化鈦的訊號來幫助我們了
解長膜機制，發現金屬奈米多層膜在鍍膜過程中會有奈米粒子溶出及回鍍的現
象。此一現象已能解釋為何奈米多層膜為一混雜，而非均勻的層狀結構。
Time-of-flight secondary ion mass spectrometer (ToF-SIMS) is an analytical
technique that can be used to characterize the surface and near surface region of solids
and the surface of some liquids. ToF-SIMS could distingulish analytes with mass
resolution different by 10000 at ppma to ppba sensitivity. Top monolayer atomic or
molecular information could be determined by adjusting primary ion current density.
Chemical images with lateral resolution 100 nm or less can be obtained by using Ga+
gun. ToF-SIMS extend its applicability to broad fields such as microelectronics,
nano-technology, polymer science, life science technology, environmental analysis
and medical technology. ToF-SIMS could simultaneously provide critical chemical
information and is a multi functional state-of-the art instrument.
In chapter 2, a single hair sample preparation protocol modified from reported
method was developed and used to prepare longitudinally sectioned hair for
ToF-SIMS analysis. Preliminary results demonstrate that ToF-SIMS is capable of
providing molecular distribution of fragment ions from intrinsic constituents as well
as external chemicals like the hair dye ingredients used in this study. The observation
of pPDA and HPO4- penetrating into the internal region of hair might initiate a
renewed interest in exposure study.
In chapter 3, A model organic light-emitting diodes (OLEDs) with structure of
tris(8-hydroxyquinoline) aluminum (Alq3)/N,N’-diphenyl-N,N’-bis[1-naphthy-
(1,1’-diphenyl)]-4,4’-diamine (NPB)/indium tin oxide (ITO)-coated glass was
fabricated for diffusion study by ToF-SIMS. The results demonstrate that ToF-SIMS
is capable of delineating the structure of multi-organic layers in OLEDs and providing
specific molecular information to aid deciphering the diffusion phenomena. Upon
heat treatment, the solidity or hardness of the device was reduced. Complicated
chemical reaction might occur at the NPB/ITO interface and results in the formation
of a buffer layer, which terminates the upper diffusion of ions from underlying ITO.
In chapter 4, all-nanoparticle multilayer films were prepared by layer-by-layer
deposition of SiO2 and Al2O3 nanoparticles onto polyester (PE) substrate. The
top-most SiO2 (and Al2O3) layer was characterized using ToF-SIMS and SEM. An
element-specific homogeneity index obtained by ToF-SIMS measurement provides
clue to the formation mechanism. Experimental results from ToF-SIMS and SEM
accord well with molecular dynamics simulation results, demonstrating the potential
of using ToF-SIMS to study all-nanoparticle multilayer films.
In chapter 5, we have investigated the growth behavior in all-nanoparticle
multilayer films using a novel indicator layer by Time-of-Flight Secondary Ion Mass
Spectrometry (ToF-SIMS) detection. The all-nanoparticle multilayer films were
prepared by dipping the polyester substrate with electrostatic charges alternatively
into solutions containing three different types of nanoparticles (TiO2, Al2O3, and
SiO2). Upon the deposition of each layer, ToF-SIMS was employed to determine the
surface chemical composition of intermediate products. The intermixing extent of
TiO2 indicator layer was used to reveal the stratification of each layer. Combining
with zeta-potential measurements, the solvation and deposition of the under-layer
species in the aqueous environment during fresh layer formation was proposed as a
plausible cause for mutilayers not stratified into well-defined layers but displaying a
nonlinear growth behavior.
2024年8月12日发(作者：盘以丹)
摘要
飛行時間式二次離子質譜術(ToF-SIMS)為一可分析固體表面化學資訊的技
術。其質量解析度可達10000，且靈敏度可達ppma至ppba等級。化學影像的橫
向解析度可藉由鎵離子槍而達到100nm。飛行時間式二次離子質譜術可應用在半
導體、微電子電路、奈米科技、高分子化學、生命科學、環境分析及藥物化學。
在第二章中，單根頭髮以縱向剖面的樣品準備形式進入ToF-SIMS分析。結
果看出外來物如染髮劑的分子離子的質譜訊號，且其離子影像分佈可看出染髮劑
已侵入至皮質層。
在第三章中，我們以飛行時間式二次離子質譜術分析含有8-羥基??鋁 (Alq3)
和NPB在氧化銦錫玻璃(ITO glass)的有機發光二極體元件。初期結果發現有經熱
處理之有機發光二極體元件會在NPB/ITO界面層產生一緩衝層。另外，NPB向
ITO擴散的情形也被觀察到。
在第四章中，二氧化矽(SiO2)和三氧化二鋁(Ai2O3)的全奈米粒子多層膜被
製造出來並由二次離子質譜術觀測其化學組成和成長機制，我們求出表面元素的
均勻度，並發現其長膜機制和分子模擬結果一致。
在第五章中，我們使用一特別的材料，二氧化鈦(TiO2)奈米粒子做為基層，
再反覆將二氧化矽和三氧化二鋁鍍在其上，再針對二氧化鈦的訊號來幫助我們了
解長膜機制，發現金屬奈米多層膜在鍍膜過程中會有奈米粒子溶出及回鍍的現
象。此一現象已能解釋為何奈米多層膜為一混雜，而非均勻的層狀結構。
Time-of-flight secondary ion mass spectrometer (ToF-SIMS) is an analytical
technique that can be used to characterize the surface and near surface region of solids
and the surface of some liquids. ToF-SIMS could distingulish analytes with mass
resolution different by 10000 at ppma to ppba sensitivity. Top monolayer atomic or
molecular information could be determined by adjusting primary ion current density.
Chemical images with lateral resolution 100 nm or less can be obtained by using Ga+
gun. ToF-SIMS extend its applicability to broad fields such as microelectronics,
nano-technology, polymer science, life science technology, environmental analysis
and medical technology. ToF-SIMS could simultaneously provide critical chemical
information and is a multi functional state-of-the art instrument.
In chapter 2, a single hair sample preparation protocol modified from reported
method was developed and used to prepare longitudinally sectioned hair for
ToF-SIMS analysis. Preliminary results demonstrate that ToF-SIMS is capable of
providing molecular distribution of fragment ions from intrinsic constituents as well
as external chemicals like the hair dye ingredients used in this study. The observation
of pPDA and HPO4- penetrating into the internal region of hair might initiate a
renewed interest in exposure study.
In chapter 3, A model organic light-emitting diodes (OLEDs) with structure of
tris(8-hydroxyquinoline) aluminum (Alq3)/N,N’-diphenyl-N,N’-bis[1-naphthy-
(1,1’-diphenyl)]-4,4’-diamine (NPB)/indium tin oxide (ITO)-coated glass was
fabricated for diffusion study by ToF-SIMS. The results demonstrate that ToF-SIMS
is capable of delineating the structure of multi-organic layers in OLEDs and providing
specific molecular information to aid deciphering the diffusion phenomena. Upon
heat treatment, the solidity or hardness of the device was reduced. Complicated
chemical reaction might occur at the NPB/ITO interface and results in the formation
of a buffer layer, which terminates the upper diffusion of ions from underlying ITO.
In chapter 4, all-nanoparticle multilayer films were prepared by layer-by-layer
deposition of SiO2 and Al2O3 nanoparticles onto polyester (PE) substrate. The
top-most SiO2 (and Al2O3) layer was characterized using ToF-SIMS and SEM. An
element-specific homogeneity index obtained by ToF-SIMS measurement provides
clue to the formation mechanism. Experimental results from ToF-SIMS and SEM
accord well with molecular dynamics simulation results, demonstrating the potential
of using ToF-SIMS to study all-nanoparticle multilayer films.
In chapter 5, we have investigated the growth behavior in all-nanoparticle
multilayer films using a novel indicator layer by Time-of-Flight Secondary Ion Mass
Spectrometry (ToF-SIMS) detection. The all-nanoparticle multilayer films were
prepared by dipping the polyester substrate with electrostatic charges alternatively
into solutions containing three different types of nanoparticles (TiO2, Al2O3, and
SiO2). Upon the deposition of each layer, ToF-SIMS was employed to determine the
surface chemical composition of intermediate products. The intermixing extent of
TiO2 indicator layer was used to reveal the stratification of each layer. Combining
with zeta-potential measurements, the solvation and deposition of the under-layer
species in the aqueous environment during fresh layer formation was proposed as a
plausible cause for mutilayers not stratified into well-defined layers but displaying a
nonlinear growth behavior.