臺灣博碩士論文加值系統

現有的相關文獻大多針對磁性材料所製備之塊材來研究其應力、溫度和導磁率之間的關係，但在積層電感元件的製程實務上，由於銀線圈與磁性材料的共燒而會衍生更為複雜的情況。除了磁性元件的感值對應力和溫度的特性之外，由於應用期間，大電流會在線圈上產生焦耳熱而提升元件自身的溫度，加上磁性元件在高溫環境且長時間的作用之下，電感值會因此產生大幅滑落進而失效。有鑑於少有文章有系統地研究積層電感元件的應力、溫度和可靠度之特性，本文取用Ni-Cu-Zn鐵氧體所製備積層陶瓷晶片電感(MLCI)，以製程粗分兩部份：共燒(燒結)與電鍍，前者再分燒結後離裂改善、溫度特性分析、應力特性分析與應力消除等四個章節，後者可分為電鍍製程與可靠度改善等兩個章節，以此六個章節做深入的研究並提出可能的改善之道。
第四章是研究燒結應力所形成之離裂問題。此應力來自元件內銀線圈與磁性材料共燒的結果，再加上因電性之需求使得銀線圈的厚度大於層間的磁性材料，因而產生巨大的應力並導致離裂。我們可藉由降低銀線圈材料中的粒度來使得銀在更低的溫度開始收縮，也就是在磁性材料仍具有彈、塑性之時使之分離可降低在高溫下兩者的拉扯或相互衝擊的程度，從而改善離裂的問題。
第五章是討論熱處理對電感元件的影響，尤其是電感值。我們藉由不同溫度的熱處理條件的結果做交叉比對，我們發現溫度促使電感值產生變化有三個成份，分別是應力的釋放、磁域特性的改變與對應力敏感的電感值轉變為對磁性敏感的電感值，其中第三個成份說明應力和溫度的交互作用；同時，我們也發現零下溫度可以降低高溫熱處理後元件電感值對磁性的影響程度。我們將利用溫度循環(Thermal cycle)處理來釋放元件內之應力，做為元件內部殘留應力評估之方法。
第六章是殘留應力對電感值影響的分析。首先我們依序就磁性材料自身、銀線圈與磁性材料之共燒，以及端電極燒結和電鍍製程，研究這些材料在製程當中產生應力並且與原有應力產生交互作用的過程。接著，我們也提出電感感值與應力的特性曲線，除了可用以解釋元件在製程當中其電感值變化與應力的變化之外，同時也說明若無法有效避免應力的產生時，在電感值對應力穩定的觀點來說，讓元件內部殘有壓應力會相對比較有利。同時，我們也藉由設定不同結構之電感元件以及對這些元件施加熱處理(冷熱循環)的實驗，來解析元件內部不同部位的應力狀態以及應力可能釋放的位置。結果顯示，應力存在於不同材料或構件之間界面，例如銀線圈與磁性材料、銀端電極與元件本體、錫/鎳/銀端電極之間界面，這些應力的分佈並不均勻，藉由局部、小規模地破壞之間的界面狀態，應力可以因此釋放。
第七章則是提出完全避免應力產生的可能作法。承第四章的研討過程，我們瞭解燒結殘留應力的來源是鐵氧體與銀金屬共燒所致，並可利用我們研究當中所發展出銀在更低溫的收縮使之和磁性材料分離的概念，也就是嘗試利用加印一層碳層在銀線圈與磁性材料之間做為隔離之用，來達成在燒結當中使銀線圈和磁性材料分離收縮，藉以完全避免應力的形成與殘留。但此一作法仍有相關製程之問題必須克服。
第八章重點則是電鍍製程後電感值變化的解析。我們藉由純磁性材料、繞線磁性材料以及晶片電感在浸泡鍍液或施以不同電鍍條件之後的電感值做交叉比對，我們發現電感值的變化有三個來源：一是鍍層的外覆產生外加應力與原有應力的交互作用，若應力的相加則電感值下降，若應力相抵則電感值上升；二是電鍍電流在電鍍當中產生磁場，進而在元件之磁性材料之上發生殘磁，此得電感值下降；三是鍍液對端電極與元件本體界面的腐蝕使得電感值上升，不儘如此，當燒結條件改變後也會連帶改變元件表面的緻密度與潤濕力狀態進而改變腐蝕的作用。
第九章是可靠度失效的分析與改善。我們藉由銅元素在端電極上析出的發現，確認了電鍍當中鍍液和元件本體有離子交換，而因此進入元件本體表面，這些外來的粒子會在高溫、有載的可靠度條件中遷移到元件內部，使得元件產生不可逆的質變因而失效。此一現象除了可以改變電鍍條件降低鍍液對元件本體的腐蝕外，利用燒結條件使元件本體表面更為緻密化，也可以有效改善此一問題，並且有效維持原有的鍍層品質。

A huge residual stress is generated in sintering process and interacts with stresses generating in following processes of manufacture of multilayer chip inductors, and this complicated stress system impacts the characteristics and limits the application of this type of inductor. Besides the stress, the current passes through coil and produces joule heat to increase the MLCIs’ (Multi-Layer Chip Inductors) temperature during working period, as time goes by, the inductance of the components within defect will lower and fail. To achieve the future demands in higher power and smaller size, the interaction mechanism, the effectiveness and the origin of inductance-stress-heat of MLCIs should be researched systematically and completely. In this dissertation, we chose Ni-Cu-Zn ferrite as a material for MLCIs and divided whole experiment into 2 major parts which are co-firing (sintering) and plating process. The first part has 4 chapters including crack, thermal characteristic, stress characteristic and eliminating stress, and second part has 2 chapters including plating and reliability. We attempted to find the root causes, mechanism and the solutions for improving MLCIs’ performance further through the studies of these 6 chapters.
The chapter 4 is dealing with relation with stress which causes the crack of MLCIs. In this study, we found the stress is generated by mismatch of silver coil and ferrite core during cofiring, furthermore, due to the need of low DCR (Direct Current Resistance) of coil, the thickness of coil is increased, and it will cause mismatch and stress even larger. By recognizing the root causes, we can select finer silver particles as the raw material of coil to make the silver coil shrink at lower temperature which the ferrite is still in ductile status, and therefore to lower the impact level to ferrite core and the crack can be inhibited.
The chapter 5 is the study of the temperature effect to the MLCIs. We arranged different temperature conditions and crosschecked their results, we found 3 parts co-contributing to change of inductance, they are stress releasing, magnetic domain change and exchange between stress-sensitive inductance and magnetic-sensitive inductance, and the third part also revealed a phenomenon that the interaction between stress and temperature. We also found that the influence of thermal treatment to the inductance relating magnetic field of MLCIs can be reduced by a pre-treatment undergoing sub-zero temperature condition. In this study, we utilized temperature cycling (TC) to release the residual stress for evaluating its level inside the MLCIs.
We studied the influence and origin of stresses which are caused by manufacture processes in chapter 6. The materials of circular type cores and multilayer chip inductors (silver coil and ferrite core co-exit inside the components), and the processes of termination making (dipping and firing process) and electroplating were all studied in sequence to indentify each contribution and their interaction in these materials and processes. We also proposed a characteristic plot of inductance-stress to elaborate the trend of inductance change following with the processes. The plot also revealed that if the stress can not be avoided inside the MLCIs, the compressive stress is preferable in the perspective of ratio of induction and stress. By utilizing different construction of multilayer chip inductors and temperature cycling handling, we can analyze the local stress status in different location and the location where the stress released. The result showed that the stresses are located in the interfaces of silver coil-ferrite core, end termination-body and Sn-Ni-Ag plating layers. The levels of these stresses are not equal, and they can be eliminated by undermining the connection of interfaces locally and limitedly.
We proposed solutions to avoid the stress completely in chapter 7. As the analysis in chapter 4, the residual stress after sintering is caused by shrinkage mismatch of silver coil and ferrite core, and therefore we can utilize a concept which is “shrinking separately” by making silver shrink at lower temperature. Furthermore, by extending the concept of shrinking separately, we developed an alternative approach which applied carbon layer under and below the silver layer to prevent the direct contact from silver coil and ferrite core to achieve the shrinking separately and the residual stress-free. However, some side effects of process are remained to be overcame.
The chapter 8 is an analysis of inductance change after electroplating of MLCIs. Comparing and crosschecking the inductances of pure ferrite coil, winding-ferrite core and MLCIs which underwent soaking plating solution and alternatively electroplating conditions, we found that there were 3 factors contributing the change of inductance, they are (1) the plating layer covered the body and generated an excess stress and interacted with residual stress inside the body, the inductance will increase when the stresses counteracts and the inductance will decrease when the stress accumulates; (2) plating solution corrodes and undermines the interface between end termination and body to release the stress and then increase the inductance, moreover, when the surface status of chip inductor are changed by different sintering profiles, the wetting ability will be changed and as well as the corrosion; (3) the current electroplating generates a magnetic field and interacted with remanence of chip inductors and caused the inductance fell.
In the last chapter (chapter 9) of the dissertation, the reliability failure was analyzed. What we found was the Cu precipitating on the end termination and we deduced that the existence of ions/ matter exchange during electroplating. By matter exchanging, the ions of plating solution penetrates into the surface of chip’s body, and then migrates into the chip body deeper by the electrical field in working or reliability test, and the irreversible change inside the chip body happens and causes function failure of MLCIs. To improve this failure, both changing electroplating conditions and changing sintering temperature can be taken.

摘要....................................................I
Summary……………………………………………………………………………..III
誌謝.............................................VI
List of tables………………………………………………………………………….X
List of figures……………………………………………………………………….XII
1. Introduction…………………………………………………………………………1
1.1 The evaluation of chip inductors…………………………………………………1
1.1.1 High frequency chip inductors………………………………………………..1
1.1.2 SMD type power inductors……………………………………………………2
1.1.3 The development trend of chip inductors……………………………….3
1.2 Motivation of the study…………………………………………………………..3
2. Theory and Technique………………………………………………………………4
2.1 Crystal lattice structure and characteristics of Ni-Cu-Zn ferrites………………..4
2.2 The categories and application of ferrites………………………..7
2.2.1 Mn-Zn ferrites………………………………………………………………...7
2.2.2 Ni-Zn ferrites………………………………………………………………….8
2.3 The processes and designs of multilayer type power inductors (MLCIs)………10
2.3.1 The impurity of raw materials……………………………………………….10
2.3.2 The preparation of slurry/ slip……………………………………………….10
2.3.3 The printing process and construction design……………….12
2.3.4 Sintering……………………………………………………………………..18
2.3.5 Plating………………………………………………………………………..18
2.4 The stress dependences of MLCIs………………………………………………19
2.5 The temperature dependences of MLCIs……………………………………….22
2.6 The reliability of MLCIs………………………………………………………..23
3. Materials and methods…………………………………………………………….26
3.1 Raw materials…………………………………………………………………...26
3.2 Fabrication procedures………………………………………………………….26
3.2.1 Chip type samples..........................26
3.2.2 Circular type samples..............................27
3.3 Characteristic evaluation and material/ microstructure analysis procedures…..28
3.3.1 Chapter 4…………………………………………………………………….28
3.3.2 Chapter 5…………………………………………………………………….28
3.3.3 Chapter 6…………………………………………………………………….29
3.3.4 Chapter 7…………………………………………………………………….31
3.3.5 Chapter 8…………………………………………………………………….31
3.3.6 Chapter 9…………………………………………………………………….32
3.3.7 Characteristic evaluation and analysis instruments..........33
PART 1. CO-FIRING PROCESS (SINTERING)……………………………………34
4. Crack of MLCIs…………………………………………………………………35
4.1 Result and discussion…………………………………………………………...35
4.2 Conclusion………………………………………………………………………40
5. The thermal characteristics of MLCIs……………………………………………..41
5.1 Result and discussion…………………………………………………………...41
5.2 Conclusion………………………………………………………………………56
6. The stress induced by construction and process conditions of MLCIs……………58
6.1 Result and discussion…………………………………………………………...58
6.2 Conclusion………………………………………………………………………71
7. Reducing the residual stress of sintering of MLCIs……………………………….73
7.1 Result and discussion…………………………………………………………...73
7.2 Conclusion………………………………………………………………………80
PART 2. PLATING PROCESS………………………………………………………81
8. The inductance change of plating process………………………………………82
8.1 Result and discussion…………………………………………………………...82
8.2 Conclusion………………………………………………………………………90
9. The reliability of MLCIs…………………………………………………………..91
9.1 Result and discussion…………………………………………………………...91
9.2 Conclusion……………………………………………………………………….104
10. Conclusion and future work.......................105
Reference……………………………………………………………………………106

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