導熱介面材料(Thermal Interface Materials, TIM)是所有電子相關產品不可或缺的組成元素之一，沒有了它，市面上就不會有電腦、遊戲機、智慧型手機，也不會有電視機、LED燈，更不會有油電混合車；既然如此不可或缺，但它卻又不造就了是電子產業慣例定義中的關鍵零組件。如此特殊的屬性與定位，導熱介面材料的不凡與平凡。 台灣廠商高柏科技過去十年，趁著消費性電子產品的興起，投入導熱介面材料的生產與銷售，並且堅持自行研發產品，十年間已見規模。但是由於小廠迅速冒出，削價競爭，殺戮慘烈，平凡的低階產品市場已成紅海。有鑑於全球總體的大趨勢，節能減碳需求與日俱增，導熱、散熱等熱管理產業已然成為下一波的主流市場，高柏科技是否可再一次順應潮流，再創另一個豐收的十年，全球競爭力的提高將是成敗關鍵。 高柏科技於是亟思運用既有核心競爭優勢，輔以積極開闢海外市場，希望以全球佈局的高度，以敏銳的市場洞察力，察覺導熱介面材料下一個世代的產品應用之星，找到一片屬於導熱介面材料的不凡的深湛藍海。 / Thermal Interface Materials (TIM) is one of key components in many electronics applications. TIM generally works to solve thermal issues in these electronic products. T-Global Technology Co., one of the top 15 leading companies in the global TIM industry, has been building its own brand by manufacturing and marketing it own products since 10 years ago. The company faces much higher competitions from producers of emerging markets who focus on the low-cost or entry-lever productions. This study considers and investigates how to develop sustainable growth strategies in the current situation. A thorough analysis suggests that strategies of deeper penetrating and expanding into global markets by leveraging the company's core competence may well serve the purpose.

找尋新穎的熱電材料是現在許多物理、化學以及材料學家的熱門研究，熱電材料的益處在於可將生活中所產生的廢熱轉化成電能再度利用，可應用在於熱機或是冷凍機之上。 首先，在第一個研究之中，透過布理奇曼法在1050 ℃之下維持10個小時用以製作Cu0.01Bi2Te2.7Se0.3塊材，以及透過水熱法製造出Cu0.01Bi2Te2.7Se0.3奈米粒子，並且將兩種不同尺寸的粒子做不同比例的混合：奈米粒子(粒徑：20~100奈米)重量百分比0、10、20、30和100；接著探討火花電漿燒結法及奈米聚合物對熱電性質之影響。在實驗中發現材料中混入百分之三十的奈米粒子可提升熱電優質係數約一倍，由0.35提升至0.74。若是可以將起初塊材的熱電優質係數提升至較良好的0.7以上，再透過奈米聚合和燒結，其熱電係數在400 K左右是可以超過1的。由這個研究顯示出：火花電漿燒結以及奈米聚合是可以有效的提升熱電優質係數，其主要原因來自於成功的降低熱傳導係數並同時維持住原本所擁有的電阻率以及席貝克係數的提升，而熱傳導降低因於樣品中的奈米結構所造成的粒子邊界增加、晶格的不匹配導致抑制聲子的傳熱所形成的結果。 第二個研究為一樣是透過布理奇曼法在750 ℃之下維持12個小時用以製作BixSb2-xTe3塊材，其中x分別為0.4、0.45、0.5以及0.6，本實驗主要為探討Bi的量對於BiSbTe所造成的影響。由結果中顯示x高於0.5和低於0.5所呈現的熱傳性質的趨勢有些許不同。在x為0.45的塊材中，得到本實驗中在室溫之下，最佳的熱電優質係數1.5，獲得此結果的主要原因來自於相對較低的電阻率，並可觀察到x為0.45的載子濃度高於0.4、0.5和0.6的結果，其將可以佐證x=0.45塊材的低電組率所造成的優質係數提升。 / Physicists, chemists and material scientists at many major universities and research institutions throughout the world are attempting to create novel materials with high thermoelectric (TE) efficiency. It will be beneficial to harvest waste heat into electrical energy. Specialty heating and cooling are other major applications for this class of new TE materials. In the first study, bulk and nanoparticles of Cu0.01Bi2Te2.7Se0.3 were prepared separately. The Cu0.01Bi2Te2.7Se0.3 bulk was fabricated by Bridgeman method at 1050 ℃ for 10 hrs and the nanoparticles were made through hydrothermal method. Two kinds of powders were mixed with the ratios of NPs 0, 10, 20, 30 and 100 wt% and sintered by the SPS technique to form the composite specimens. The ZT value can be enhanced over 100% from 0.35 to 0.74 for specimen with 30 wt% nanoparticles. The consequence indicates that the SPS process and mixing nanocomposite can effectively enhance ZT value. The enhancements were caused mainly by the presence of nanostructured regions existing within the samples which lowered the thermal conductivity. The phenomenon is due to the presence of significant number of grain boundaries, shorten phonon mean free path and lattice mismatch. For another investigation, the BixSb2-xTe3 ingots with x=0.4, 0.45, 0.5 and 0.6. were fabricated by Bridgeman method at 750 ℃ for 12 hrs. We studied the effects of amount of Bi in BixSb2-xTe3 and the SPS process on the ZT enhancement. The experiment showed that for x >0.5, the thermal property changed from a curve to a relatively linear line at the end. The best ZT is 1.5 ingot at 300 K for x=0.45 specimen. The significant ZT improvement arises from the much-reduced electric resistivity. The lowest resistivity for x=0.45 specimen is mainly due to the highest carrier concentration than those with x=0.4, 0.5 and 0.6 ingots.

学位授与大学：京都大学 ; 取得学位: 博士(工学) ; 学位授与年月日: 2007-09-25 ; 学位の種類: 新制・課程博士 ; 学位記番号: 工博第2866号 ; 請求記号: 新制/工/1421 ; 整理番号: 25551 / The developments in microstructure and phase structure of Sn-based materials gave stable cyclability under the full charge and discharge conditions without the initial large irreversible capacity. Some important structures discovered and their mechanisms for improving the cyclability were discussed as follows. In Chapter 1, the electrode structure of Sn electrodes was discussed, where the theoretical capacity of Li4.4Sn was attained. Weak adhesion of Sn to the Cu foil prevented the powdered Sn electrodes prepared by a conventional slurry-coating process from providing the theoretical capacity of Sn metal from the initial cycle, where the Sn powder peeled off the Cu foil to be disconnected from the foil in electronic conductivity. The electrodeposition process improved the interface adhesion between Sn and Cu foil. The electrodeposited Sn film sticks tightly to the Cu foil after forming the intermediate Cu6Sn5 layer, and it reacts with lithium to the theoretical capacity of Li4.4Sn under the full charge-discharge condition with small irreversible capacity. The initial discharge capacity was 2.5 times as large as that of the graphite. In Chapter 2, the advanced phase structure of the electrodeposited Sn film was discussed, which improved the film in cyclability without a large loss of capacity. The Sn film-Cu foil interface adhesion was still weaker to be delaminated from the Cu foil. Also, the Sn film was pulverized and passivated by electrolyte reduction products. The film was disconnected from the Cu foil in electronic conductivity during the initial cycle and could not continue to react with lithium. The stepwise composition-graded phase structure improved the film in the interface adhesion and active material chemistry to provide better cyclability under the full charge-discharge condition without large sacrifice of their volumetric capacity. The phase structure consists of the Cu6Sn5 and Cu3Sn phases, where Cu6Sn5 phase is the active material with less volume change and electrolyte-reactivity and the Cu3Sn phase enhances the adhesion between the Cu6Sn5 phase and Cu foil. The annealing process formed the stepwise composition-graded phase structure, and the annealing condition controlled the structure to be optimized for better cyclability. In Chapter 3, the advanced microstructure of the electrodeposited Sn film was discussed, which improved the film with the stepwise composition-graded phase structure in cyclability. The annealed rough-surfaced Sn electrode showed better cyclability than the annealed flat-surfaced Sn electrode, even though they had the same stepwise composition-graded phase structure. The micro-columnar structure of the film improved the film in the interface adhesion. The structure self-organizes on the rough surface of the Cu foil during the first charge-discharge cycle. The film is divided into columns of about 10μm square by gaps to accommodate swelled film with much reduced internal stress and strain during the following charge, resulting in less pulverization and enhanced adhesion of the film to the foil. The wavy surface profile of the foil and moderate ductility of the film are critical factors to self-organize the micro-columnar structure of the film during charge and discharge. Close cyclability to typical graphite-anode cells was available for the small cell using the annealed rough-surfaced Sn electrode for 20 cycles. In Chapter 4, the electro co-deposited 79.8Sn-20.2Co alloy film was examined for electrochemical and structural properties, and the feasibility of formation of the microstructure was discussed. The micro-island structure was self-organized on the rough surface of the Cu foil during the first charge-discharge cycle, which is similar to the micro-columnar structure in mechanism for improving the cyclability as well as in the shape. As a result, the Sn-Co alloy electrode offered the same capacity at the 20th cycle as the initial capacity of about 60% of the theoretical capacity of Li4.4Sn. The mechanical properties of the film such as ductility and brittleness give another key for formation of the microstructure, in addition to the rough surface of the current collector foil. In Chapter 5, the anomalous cycle performance of the 79.8Sn-20.2Co alloy electrode was discussed in terms of morphology and phase structure of the film. The film showed four-step change in discharge capacity, which depends on the two-stage phase transformation and morphological change of the film. The film is transformed from the amorphous phase to a new phase with forming fcc-Co particles. The new phase is a key to stable reaction of the Sn-Co film with lithium. Although the new phase initially shows smaller capacity than the amorphous phase, the enlarged surface area of the film activates a new reaction of the new phase to increase capacity. As a result, the new phase provides as large capacity as the amorphous phase. In Chapter 6, the electro co-deposited 92.1Sn-7.9Co alloy film with the microstructure was examined for electrochemical and structural properties, which comprised the new phase of the 79.8Sn-20.2Co alloy film as electrodeposited, and the mechanism of the reaction stability of the new phase was discussed. The 92.1Sn-7.9Co alloy film had the nano-composite phase structure, where the less lithium-active crystalline phase surrounds the amorphous phase to accommodate volume change of the amorphous phase and prevent it from deteriorating, resulting in stable reaction of the amorphous phase with lithium to provide constant capacity. On the other hand, the morphological and phase structural changes of the film improve Li+ diffusion through the film-electrolyte interface, in the film, and in the amorphous phase to increase capacity. As a result, under the full charge-discharge condition, the 92.1Sn-7.9Co alloy film showed monotonous increase in discharge capacity from 663 mAh/g at the 1st cycle to 769 mAh/g at the 20th cycle, which is 77% of the theoretical capacity of Li4.4Sn. Since the phase transformation of the 79.8Sn-20.2Co alloy film caused deterioration of the adhesion between the film and current collector to degrade the cyclability of the film, the phase structure of the 92.1Sn-7.9Co film gives better cyclability when it is prepared in advance of the reaction. There should be still room for further stable cyclability in Sn-Co alloy films. For example, adding a third atom to the film composition may enhance the stability of the reaction of the amorphous phase. Not only electro co-deposition but various thin-filming processes will be proposed to control a three-or-more-component system. However, the adhesion of the film and Cu foil is the crucial factor for the stable cyclability, and the microstructure such as the micro-columnar structure and micro-island structure is the most fundamental and effective in enhancing the adhesion. The micro-columnar structure has been applied for Si and Ge systems and examined for its self-organization mechanism, cyclability, and other electrochemical properties. Some of the results have already reported [67-68]. The advanced lithium ion batteries of group 14 elements with the microstructure may become commercially available in near future. Also, the microstructure should be formed on the flat-surfaced foil with holes in the same stress-concentration mechanism as the rough-surfaced foil. Since the rough-surfaced Cu foil is formed by Cu electrodeposition, there are limitations to control the surface profile. However, the holes can be punched at intervals of a-micrometer-order by using physical processes such as a femto-second laser, resulting in formation of further size-controlled microstructure. Issues of the laser process are beam concentration to make holes of less than 10μm in diameter and long work time. A suitable grating should be a key to overcome the issues and find another potential of the microstructure. / Kyoto University (京都大学) / 0048 / 新制・課程博士 / 博士(工学) / 甲第13395号 / 工博第2866号 / 新制||工||1421(附属図書館) / 25551 / UT51-2007-Q796 / 京都大学大学院工学研究科材料化学専攻 / (主査)教授 平尾 一之, 教授 横尾 俊信, 教授 田中 勝久 / 学位規則第4条第1項該当

Kyoto University (京都大学) / 0048 / 新制・課程博士 / 博士(工学) / 甲第14164号 / 工博第2998号 / 新制||工||1445(附属図書館) / 26470 / UT51-2008-N481 / 京都大学大学院工学研究科材料工学専攻 / (主査)教授 杉村 博之, 教授 粟倉 泰弘, 教授 酒井 明 / 学位規則第4条第1項該当

Kyoto University (京都大学) / 0048 / 新制・課程博士 / 博士(工学) / 甲第16390号 / 工博第3471号 / 新制||工||1525(附属図書館) / 29021 / 京都大学大学院工学研究科建築学専攻 / (主査)教授 上谷 宏二, 教授 田中 仁史, 教授 西山 峰広 / 学位規則第4条第1項該当

Kyoto University (京都大学) / 0048 / 新制・課程博士 / 博士(工学) / 甲第16399号 / 工博第3480号 / 新制||工||1526(附属図書館) / 29030 / 京都大学大学院工学研究科材料工学専攻 / (主査)教授 松原 英一郎, 教授 杉村 博之, 准教授 邑瀬 邦明, 教授 中村 裕之 / 学位規則第4条第1項該当

Kyoto University (京都大学) / 0048 / 新制・論文博士 / 博士(工学) / 乙第12651号 / 論工博第4079号 / 新制||工||1547(附属図書館) / 29729 / (主査)教授 平尾 一之, 教授 田中 勝久, 教授 三浦 清貴 / 学位規則第4条第2項該当

近幾年來，熱電材料蓬勃發展是許多物理、化學以及材料科學家的熱門研究的方向，然而此一跨領域的基礎研究工作處於萌芽的階段。熱電材料的益處在於可將熱機或是冷凍機之上所產生的廢熱轉化成電能。本研究利用鉍化碲(Bismuth Tellurium)在室溫附近具有一熱電優質係數(ZT)為1.0的熱電表現，其具有非常低的熱傳導率以及適當的載子傳輸性質，因此Bi-Te的合金系列成為大家研究的趨勢，成為另一項重大的焦點引發相當的關注。鉍化碲元素皆是地球殼中豐富的元素，且鉍化碲是對人無毒且對環境無害的化合物，相較於其他高性能熱電材料(一般由稀少元素/貴金屬組成)，具有非常大商業化的潛力。鉍化碲本身為非常穩定的多層層狀結構(Quintuple Layer)，表現出極低的熱傳導率以及良好的導電性。為了未來能製作出微小的熱電模組，本研究利用射頻磁控濺鍍系統(Radio-Frequency Magnetron Sputtering System)調控濺鍍參數的方式，得到最佳熱電性質之薄膜後，再使用半導體製程技術製作微結構的陣列熱電薄膜，利用光微影製程及金屬遮罩兩種分別不同的方式決定所需之電極和薄膜陣列之圖形。本論文使用磁控濺鍍設備，靶材n-type和p-type分別選用Cu0.02Bi2Te2.7Se0.3 和Bi0.5Sb1.5Te3+0.33 wt% Aerogel之熱電材料，經由實驗改變磁控濺鍍的工作壓力、RF power，再透過ZEM-3、EDS對薄膜的研究分析得到(最佳鍍膜參數) 最佳鍍膜品質參數(seebeck、電阻)。決定鍍膜參數後使用本研究開發的兩種方式製作微結構熱電元件，一使用光微影半導體製程，二使用金屬遮罩，針對兩種製程方式所得的n-type和p-type陣列熱電薄膜成長過程做比較與研究探討。 / In recent years, physicists, chemists and material scientists at many major universities and research institutions throughout the world are attempting to create novel materials with high thermoelectric (TE) efficiency. It will be beneficial to harvest waste heat into electrical energy. Especially heating and cooling are other major applications for this class of new TE materials. At present the thermoelectric (TE) material bismuth telluride (Bi2Te3) baesd systems exhibit best figure of merit (ZT). Bismuth and tellurium are earth-abundant elements and Bi2Te3 is non-toxic to human beings and the environment. Therefore, it has great potential in commercial implements. Bismuth telluride is a quintuple layer-structured compound possessing ultralow thermal conductivity and moderate electrical conductivity. In this work, the TE thin film and device are fabricated and optimized by Radio-Frequency Magnetron Sputtering System (RFMSS) and the influence of the preparative parameters such as working pressure and working power of RF sputtering are investigated. In this study, we used the magnetron sputtering equipment and the thermoelectric materials n-type target and p-type target were Cu0.02Bi2Te2.7Se0.3 and Bi0.5Sb1.5Te3+0.33 wt% aerogel, respectively. In this study, the experimental changes the magnetron sputtering working pressure, RF power before the ZEM-3, EDS analysis the thin film thermoelectric properties to get the best thin film quality parameters (Seebeck coefficient, resistivity, power factor). After the thin film parameters were determined, the microstructural thermoelectric 442 pairs device were fabricated by the photolithography semiconductor process, and n-type and p-type arrays used by photolithography to define a pattern and deposit Au electrodes onto the substrate by thermal evaporation.

京都大学 / 新制・課程博士 / 博士(工学) / 甲第23186号 / 工博第4830号 / 新制||工||1754(附属図書館) / 京都大学大学院工学研究科都市環境工学専攻 / (主査)教授 高岡 昌輝, 教授 米田 稔, 准教授 大下 和徹 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DGAM

京都大学 / 0048 / 新制・論文博士 / 博士(工学) / 乙第12928号 / 論工博第4121号 / 新制||工||1626(附属図書館) / 32138 / (主査)教授 平尾 一之, 教授 田中 勝久, 教授 三浦 清貴 / 学位規則第4条第2項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DFAM