銅擴散在銀(鋅/錫)與受壓力鈀薄膜之研究

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姓名

林而儒(Erh-Ju Lin) 查詢紙本館藏

畢業系所

化學工程與材料工程學系

論文名稱

銅擴散在銀(鋅/錫)與受壓力鈀薄膜之研究
(Cu diffusion in Ag(Zn, Sn) and stressed Pd thin films)

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至系統瀏覽論文 (2025-8-19以後開放)

摘要(中)

在不影響線寬的前提下，3D IC可藉由垂直堆疊減少訊號傳輸路徑及均勻電流以增強訊號強度。為了避免固-液系統高鍵合溫度的製程產生的脆性界金屬化合物導致銲點可靠度不佳的問題，低溫固態交互擴散鍵合為關鍵技術。目前常用的銅銅擴散鍵合技術在鍵合過程中介面易氧化，導致接合品質不佳，因此需要抗氧化層的保護；其中鈀除了不易產生氧化反應、與銅沒有飽和溶解度的限制等優點，故此研究中，選用鈀金屬作為抗氧化層。此外，在低溫固態交互擴散鍵合的過程中，為有效降低鍵合溫度，鍵合過程中常施予適當之單軸壓力於材料上；然而相較於在過去被大量研究的三軸等壓對擴散的影響，單軸壓力的效應鮮少被提及，因此單軸壓力對於降低鍵合溫度達到良好的接合界面具有高度的研究價值。首先使用熱蒸鍍將鈀金屬化於鍍製的銅(220)優選面後置入石墨製具，施於垂直方向0 MPa, 125MPa 及250 MPa的單軸加壓熱退火實驗。透過Ar離子蝕刻與XPS元素分析，我們可以得到在不同退火時間、溫壓系統的Pd/Cu交互擴散縱深元素分布，並利用Boltzmann-Matano methods求得交互擴散係數後將(1) Erying equation基態與活化態的能差關係與(2)原子在固態晶體中三維簡諧震盪行為導入擴散行為進行討論。從實驗求得的活化焓與活化火商可以透過基態與活化態的動能差與震動火商回歸出的半經驗式應用於單軸壓力及退火溫度對於低溫固溶體交互擴散行為的預測。
GaN LED的可靠度中，固態鍵合製施予的熱及元件使用過程產生的廢熱皆會產生反射率大幅下降的現象，因此我們選用鋅與錫利用蒸鍍機鍍製銀(鋅/錫)合金，透過XPS表面的元素濃度分析與分峰，討論熱處理過程中(1)銀及銀(鋅/錫)合金表面的氧化物組成對反射率下降的影響，並透過XPS縱深元素濃度分布與分峰計算出(2)在銀/及銀(鋅/錫)合金層中的銅通量。

摘要(英)

3D IC can reduce the signal transmission path, vertical current conduction and uniform current by vertically stacking to enhance signals. In order to avoid the reliability problems of using a solid-liquid system at high bonding temperature to cause the brittle IMC formation at the joints in 3D IC, low-temperature solid-state interdiffusion bonding is a key technology. However, the common Cu-Cu diffusion bonding is easy to oxidize during the process, resulting in poor quality. Therefore, an anti-oxidation layer is needed. Pd is hard to oxidize and form solid solution with Cu. Further, in order to effectively reduce the bonding temperature, uniaxial stress is applied to the materials during the bonding process; however, comparing with the hydrostatic pressure which has been extensively studied in the past, the effect of uniaxial axial stress is rarely mentioned. Therefore, the uniaxial axial stress effect has high research values for promoting the phenomenon of interdiffusion to achieve a good bonding interface at low temperature. First, the Pd is metallized on the electro-plated Cu (220) by evaporation deposition, and placed in the special graphite cell with 0 MPa, 125 MPa, and 250 MPa in vertical direction. Through Ar ion etching and XPS element analysis, we can obtain the Pd/Cu interdiffusion depth distribution in different temperature and uniaxial axial stress, and use the Boltzmann-Matano methods to obtain the interdiffusion coefficients. Then, the relationship between the energy difference between (1) Erying equation ground state and activated state and (2) the 3-D harmonic oscillation of atoms in solid crystals are introduced into the diffusion behavior for discussion. The activation enthalpy and entropy obtained from the experiments can be used to predict the interdiffusion behavior of low temperature solid solutions by uniaxial axial stress and temperature effects through the regression of the difference in kinetic energy and vibrational entropy between the ground and the saddle state.
In the GaN LED reliability problems, due to the heat production from the solid-state bonding process and device working, the reflectance of plated Ag lead frame would decrease dramatically. We use Zn and Sn alloy with Ag in evaporation deposition, and discuss the effects of the oxide composition on (1) the resistance of reflectance decay by the element concentration analysis and peak separation on the Ag and Ag(Zn/Sn) surface and (2) the copper flux in the Ag and Ag(Zn/Sn) alloy layer by calculated the XPS depth element concentration distribution and peak splitting.

關鍵字(中)

★ 銅鈀合金
★ 交互擴散
★ 單軸加壓鍵合
★ 銀合金
★ 抗反射率下降

關鍵字(英)

論文目次

Abstract (Chinese)......................................i
Abstract (English).....................................ii
Table of contents.....................................iii
List of figures........................................iv
Chapter 1: Background...................................1
1.1 Introduction of solid-state diffusion............1
1.2 Mathematical equations and analysis techniques in
solid-state diffusion...........................3
1.3 Vacancy mechanism in solute-state diffusion......5
Chapter 2: Motivation..................................12
2.1 Bonding technology in vertical 3D-IC and thin-GaN
vertical LED....................................9
2.2 Pd-Cu binary solid-solution system..............12
2.3 Reliability of the Ag and Ag alloy coated lead
frame and reflector cup........................13
Chapter 3: The experiments procedure and analysis methods
............................................16
3.1 Pd/Cu interdiffusion under uniaxial compressive
stress.........................................16
3.2 Pd/Cu interdiffusion coefficients and activation
parameters calculation.........................17
3.3 Experimental procedure for the Ag/Cu reliability
...............................................18
3.4 Method to estimate Cu Flux in Ag, Ag(Zn, Sn)
during annealin................................19
Chapter 4: Uniaxial compressive stress effect on
interdiffusion..............................22
4.1 Results and discussions on interface movement and
intrinsic diffusivity..........................22
4.2 Mechanism of uniaxial stress on interdiffusion
activation enthalpy............................27
4.3 Mechanism of uniaxial stress on interdiffusion
activation entropy.............................31
Chapter 5: Cu flux in Ag, and Ag(Zn, Sn)...............34
5.1 Ag and Ag(Zn, Sn) reflectance and XPS depth
profile results................................34
5.2 Optical property of oxides and reflectance decay
after annealing................................39
5.3 Calculation of Cu flux in Ag, Ag(Zn, Sn) during
annealing......................................41
Chapter 6: Summary.....................................52
6.1 Summary of uniaxial compressive stress effect on
interdiffusion.................................52
6.2 Summary of alloying Ag effect on reflectance
decay..........................................52
References.............................................53

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指導教授

劉正毓

審核日期

2020-8-20

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