201136949 六、發明說明： 【發明所屬之技術領域】 v 本發明係關於一種高度交聯類聚內稀材料 ，(cross_linkeci p〇1ypr〇pylene-Hke material)以及製造 該材料之方法。較佳的實施例係關於具有可控制介電常數 α值)之高度交聯聚丙烯材料’其可調整至相對低的介電 係數（permittivity)(例如相對於二氧化矽），並可表現出 接近於陶竟的機械性質。此高度交聯聚丙烯材料適用於微 電子製造的用途，以及廣泛應用於保護、濁滑性以及負载 車由承塗覆，及許多其他用途。這些用途包含光電子應用， 其中可利用其可調整的介電性質。 【先前技術】 材料的介電常數表示當施加電勢（pGtential)穿透此 材料時所儲存的能量。定義相對於储存能量在真空中以及 有時指相對材料的靜態介電係數。介電常數通常由符號 ει*或k表示’但在微晶片製造領域中通常用k表示，而 且在本文中採用此命名，將介電常數稱為“ k值”。 在微日日片中，”電層δ又置於導電部件（例如導線以及電 晶體）之間。關於驅動微型裝置運轉，介電層會較薄，且導 電《卩件則較緊密靠近。在高操作頻率下，各種電子元件間 的電容性串音（capacitive cr〇ss—talk)限制了切換頻 率，並進一步產生廢熱而限制了熱效能。 穿過介電層儲存的電容性電荷，係直接與介電層形成 材料的介電常數（k值）成正比。因此，具低介電常數的材 94932 3 201136949 料能加快切換頻率，以及減少熱損失與串音（crosstaik)。 傳統上，用二氧化矽（SiOO以及氮化矽（Si3N4)形成矽 微aa片中的介電詹。這些材料相當適合於半導體微晶片製 造製程’而且提供低成本與可靠的解決方案。然而，Si〇2 及ShN4本身的k值被認為過高，且通常需要降低，並藉由 用夕孔性結構沉積它們或用較低k值的材料摻雜它們，以 達到較低又有效的k值。 已做過各種嘗試，去開發適合半導體微晶片用途而且 k值比Si〇2及ShN4基薄膜還低的新型介電材料。廣泛地 說，已研究過兩種材料種類：製造“硬”層的材料種類， 以及製造“軟，，層的材料種類。 硬層材料包含相對堅固的陶瓷材料’例如經摻雜的二 氧化矽、氮化矽、氧化鋁、氧化鈦以及二氧化給。此等材 料的層可經由化學氣相沉積（CVD)製造，尤其是電聚增益化 學氣相沉積（PECVD)，除了這些技術以外還有濺錢 (sputtering) ° 硬層材料的優點包含其化學一致性、相對高的崩潰電 壓（breakdown voltage)及低（熱）損失（即使在高頻下）。用 於硬層材料的製造技術也高度地可再現以及可調整於現今 的微電子材料（例如矽）。 然而，硬層材料具有數種缺點。舉例來說，此等材料 的薄膜的厚度到一些臨界值（通常為1/im左右）以上就不 容易製造’因為硬層材料與基板（硬層材料係形成在基板上） 之間的界面力會引發層裂（delamination)。此等界面力正 94932 4 201136949 比於硬層材料的厚度，並固存於常使用的PECVD沉積方法 中。尤其是，硬層材料與基板（硬層材料係形成基板上）之 間的界面承受著兩層間的整合應變（coherency strain)、 表面能差（surface energy difference)、差排能應變 (dislocation energy starin)以及硬層材料與基板間的熱 擴張速率差所造成的應力。此製造製程本身會造成熱應力 的產生或優勢，以及硬層材料層裂的發生可說是重大的問 題。此問題可藉由硬層材料與基板的熱膨脹係數相配合而 減輕，但因此嚴重地限制了材料的選擇性。 軟層材料不具這些缺點’因為它們本身存在有彈性。 此等軟層材料的範例包含旋塗玻璃（spin_〇n glass)以及 旋塗聚合物（spin-on polymer)(例如聚醯胺）。 可惜的是，旋塗聚合物通常具有相較不佳的熱穩定 性。為了改善此特性，通常需要經由如加熱或幅射的應用 來固化（cure)聚合物。典型的固化製程包括：通常在5〇〇 °C以下的溫度，依據聚合物的種類烘烤數秒至數小時的一 段時間。此SHb製程通常會產生非職的副產物，並增加 了製程的步驟以及梅延了製造製程的時間。 %塗製紅用浴劑來產生聚合物薄膜。這些溶劑在製程 期間將會蒸發’但部份溶料通常會在·後殘留在材料 中’造成材料的不-致性以及雜f。這些出現在旋塗聚合 物中的雜質限制了它們作為微晶片製造中的介電材料的庫 用’儘管實際上能達到相對低的U。尤其是，已經發現 薄膜中的水與溶劑分子會吸收射頻能量（radi。frequency 5 λ. 94932 201136949 energy)，造成操作期間的功率損失以及薄膜劣化。 於期刊Biomaterials，第7(2)卷，1986年3月，第 155 至 157 頁，“Characterisation of plasma polymerised polypropylene coatings” 文中，R. Sipehia 與 A. S.201136949 6. DISCLOSURE OF THE INVENTION: TECHNICAL FIELD OF THE INVENTION The present invention relates to a highly crosslinked polythene material (cross_linkeci p〇1ypr〇pylene-Hke material) and a method of manufacturing the same. A preferred embodiment relates to a highly crosslinked polypropylene material having a controllable dielectric constant alpha value which can be adjusted to a relatively low permittivity (e.g., relative to cerium oxide) and can be exhibited Close to the mechanical properties of Tao Jing. This highly crosslinked polypropylene material is suitable for microelectronics manufacturing applications, as well as for a wide range of applications in protection, turbidity and load bearing applications, and many other applications. These uses include optoelectronic applications in which the adjustable dielectric properties can be utilized. [Prior Art] The dielectric constant of a material means the energy stored when an applied potential (pGtential) penetrates the material. The definition is relative to the stored energy in vacuum and sometimes refers to the static dielectric constant of the opposing material. The dielectric constant is usually represented by the symbol ει* or k' but is usually represented by k in the field of microchip fabrication, and this designation is used herein to refer to the dielectric constant as the "k value". In the micro-day film, "the electrical layer δ is placed between conductive parts (such as wires and transistors). Regarding the operation of the driving micro-device, the dielectric layer will be thinner, and the conductive "pieces are closer together. At high operating frequencies, capacitive crosstalk between various electronic components limits the switching frequency and further generates waste heat that limits thermal efficiency. The capacitive charge stored through the dielectric layer is directly It is proportional to the dielectric constant (k value) of the dielectric layer forming material. Therefore, the material with low dielectric constant 94932 3 201136949 can speed up the switching frequency and reduce heat loss and crosstalk. Traditionally, Cerium oxide (SiOO and yttrium nitride (Si3N4) form a dielectric in 矽 microaa sheets. These materials are quite suitable for semiconductor microchip fabrication processes' and provide a low cost and reliable solution. However, Si〇2 and The k values of ShN4 itself are considered too high and usually need to be reduced and they are deposited by using a smectic structure or doping them with a lower k value material to achieve a lower and more effective k value. Various attempts have been made to develop new dielectric materials that are suitable for semiconductor microchip applications and have a lower k value than Si〇2 and ShN4 based films. Broadly speaking, two types of materials have been studied: the types of materials used to make "hard" layers, And the manufacture of "soft, layer material types. Hard layer materials contain relatively strong ceramic materials" such as doped ceria, tantalum nitride, aluminum oxide, titanium oxide and dioxide. Layers of these materials can be Manufactured by chemical vapor deposition (CVD), especially electropolymerized gain chemical vapor deposition (PECVD), in addition to these techniques, there is sputtering. The advantages of hard-layer materials include chemical consistency, relatively high collapse. Breakdown voltage and low (heat) loss (even at high frequencies). Manufacturing techniques for hard layer materials are also highly reproducible and can be tailored to today's microelectronic materials (eg, germanium). Materials have several disadvantages. For example, the thickness of the film of these materials is not easy to manufacture above some critical values (usually around 1/im) because of the hard layer material and the base. The interfacial force between the hard layer material formed on the substrate causes delamination. These interface forces are 94932 4 201136949 compared to the thickness of the hard layer material and are deposited in the commonly used PECVD deposition method. In particular, the interface between the hard layer material and the substrate (on the hard layer material forming substrate) is subjected to coherency strain, surface energy difference, and dislocation energy between the two layers. Starin) and the stress caused by the difference in thermal expansion rate between the hard layer material and the substrate. This manufacturing process itself can cause thermal stress generation or advantages, and the occurrence of hard layer material cracking can be said to be a major problem. This problem can be mitigated by the combination of the hard layer material and the thermal expansion coefficient of the substrate, but thus severely limits the selectivity of the material. Soft layer materials do not have these disadvantages' because they are inherently elastic. Examples of such soft layer materials include spin-on glass and spin-on polymers (e.g., polyamine). Unfortunately, spin-on polymers generally have relatively poor thermal stability. In order to improve this property, it is often necessary to cure the polymer via applications such as heating or radiation. Typical curing processes include baking at temperatures typically below 5 ° C for a period of seconds to hours depending on the type of polymer. This SHb process typically produces off-the-shelf by-products and adds steps to the process and time to the manufacturing process. % Paint a red bath to produce a polymer film. These solvents will evaporate during the process, but some of the solvent will usually remain in the material after it, causing the material to become non-cavitating and miscellaneous. These impurities present in the spin-on polymer limit their use as a reservoir for dielectric materials in the manufacture of microchips, although in practice a relatively low U can be achieved. In particular, it has been found that water and solvent molecules in the film absorb radio frequency energy (radi. frequency 5 λ. 94932 201136949 energy), resulting in power loss during operation and film degradation. In the journal Biomaterials, Vol. 7(2), March 1986, pp. 155-157, “Characterisation of plasma polymerised polypropylene coatings”, R. Sipehia and A. S.
Chawla揭露一種用於形成電漿聚合聚丙烯薄膜於基板上之 方法，其中丙烯單體於低壓下在射頻電漿反應器中聚合。 因為來自電漿的能量耦合（energy coupling)，預期經由丙 烯的聚合反應而形成聚丙烯。 在本通常領域中已被揭露的其他先前技術有美國專利 案號 US4632844、US4312575 以及 US5000831。 【發明内容】 本發明尋求提供一種製造高度交聯類聚丙烯材料之方 法以及裝置，例如包含此材料之電子電路以及光電電路。 根據本發明之一態樣，提供一種製造高度交聯聚丙稀 材料之方法，其包含下列步驟··提供反應腔室；從複數種 含碳氣體中選擇一種或多種含碳氣體；將一種或多種經選 擇之含碳氣體饋入腔室中；在腔室中撞擊電漿，此電漿使 氣體或多種氣體游離成含甲基自由基（methyl radical)2 相；造成此游離相形成核並藉以產生高度交聯聚丙烯材 料’較佳者為在高度UV輕射下進行。 有利的是，聚丙烯材料包括複數個重複結構單元的聚 合物鏈’平均每6個結構單元具有至少一個交聯，及/或複 數個跨越相鄰聚合物鏈的交聯。 已發現.相較於傳統聚丙稀，藉由本方法製成的聚丙 6 94932 201136949 烯材料表現出重大改善的特性，包含極低介電常數、良好 ^ 結構特性與高熔點，以及增強的機械穩定性。此特性使此 材料能適合各種廣泛的應用，包含用於整合電子或光電電 路的介電或絕緣層。其亦適合廣大且取多的其他應用，例 如提供保護、潤滑、負載轴承及/或抗熱塗覆。 如下列說明，可確信藉此方法製造的材料為類聚丙 烯。儘管具有三維交聯的高度影響，而且相較於傳統聚丙 烯具有改善的特性，此材料仍表現出聚丙烯的性質。此材 料因此在本文中稱為聚丙烯材料，儘管一般的理解是此定 義包含藉由所教示方法形成且具有本文在此揭露的特性的 聚合物材料。 較佳者為一種或多種經選擇之含碳氣體係選自於下列 氣體或蒸氣所組成之群組：包含乙炔、丙酮、乙烯'乙醇、 甲烷以及丙烯。最佳者為使用乙炔及丙酮的組合。在其他 實施例中，可使用單獨的乙炔或丙酮，或者，乙炔或丙酮 與任何其他氣體的混合物。 就這點而言，已經發現：在不必使用丙烯作為起始材 料的情況下，也能製造高度三維交聯聚丙烯材料。能使用 其他含碳氣體或蒸氣（vapour)。換句話說，此方法可以使 用選擇一種或多種不含聚丙烯之含碳氣體。 從各種含碳氣體的任意者產生的聚丙烯材料而已經被 發現可能是含甲基自由基的相中的含碳輸入氣體經電漿撞 擊而游離所造成的結果。此方法提供此等甲基自由基與CH 鏈分子融合，並形成高度交聯聚丙烯材料。本製程中提供 7 9493¾ 201136949 uv輻射，促進並增強了三維交聯。 此特徵有助於允許更多種輸入材料用於本製程中，因 此可=根據本製程及最終產物所需特性選擇輸入材料。 輸入氣，可包含洛氣’例如丙酮。因此須了解的是，此處 所指的氣體亦包含蒸氣。 車乂佳者，電漿具有提升聚丙烯材料中交聯產生 (production)之紫外光輻線餘。紫外光輻線成份有益地 具有在聚丙烯材料合成期間UV固化聚丙烯材料的效果。 在實際實料，此^法包含在《 +提供帛_及第二 電性電極的步驟，其中成核步驟包含於第—及第二電極間 施加電勢差（potential difference)。 在-實施例中，此方法提供置於第一及第二電極其中 -者上的基板。成核步驟包含：於第—及第二電極間施加 電勢差’以使成核材料沉積於電極上，藉以使高度交聯聚 丙烯材料之層形成於基板上。 因此’在此實施例中，聚丙烯材料直接形成於通常可 以是裝置表_基板上。基板可以是電性或電子電路的一 I5伤”中π度又^聚丙婦材料提供基板上的電性絕緣 層。換句話說’此特徵可直接在電子裝置上形成介電層，該 層展現出本文中在此所教示的特別有益之特性。 在另’、施例中’聚丙騎料可在電聚相中以粒子或 薄片形式，核，其可形容成像是“雪花（s_)，，般地生 長在本實施例中，此方法有益地包含下列步驟：收集聚 丙烯材料’以及隨後在基板㈣置上沉積材料。其可將聚 94932 8 201136949 丙婦材料懸浮或溶解在溶液中。接著可將此懸浮或溶解的 材料藉由噴塗（spray coating)、旋塗、靜電塗覆或任何其 他適合的方法沉積在基板上。 較佳者’此方法包含在腔室中提供包含至少一種補充 氣體之载送氣體（carrier gas)。補充氣體有利地包含下列 之者或多者：氫氣、氮氣、氦氣、氬氣、氙氣或其他惰 性氣體（noble gas)。補充氣體在電漿中能促使氣體成份加 強游離’藉以產生層（例如，薄膜）、薄片（flake)或粒子形 式的向度交聯聚丙烯材料。相對於選為游離用的含碳氣 體’補充氣體也能展現出高電離（ionisation)電勢。換句 $說’當提高全部電漿能量以及電漿中參與聚合物層生長 的游離種類的相對數目時，一種或多種補充氣體能有助於 確保含碳氣體可在相對低的能 量下電離。 較佳者’亦將此材料退火。已發現退火能改變或降低 聚丙細材料的介電常數。 實際上’較佳者為退火步驟在真空或氣體受控制的環 境中進行’氣體受控制的環境使用如惰性氣體之一者或惰 性氣體之組合。 有益的是，此方法包含下列步驟：在電漿成核或合成 步驟期間’藉由非電漿方式提供腔室中的額外加熱。 實際的實施例中包含下列步驟：在腔室中提供基板， 其中該基板與電極接觸；藉由施加電壓於腔室内的相對電 極（counter electrode)，而在腔室中撞擊電漿，藉以在基 fc_L形成材料層，其中電漿具有紫外光輻射成份，係增強 9 94932 201136949 在二維空間中聚合物的交聯，以對形成之材料給予機械完 整性以及熱穩定性。 根據本發明的另一態樣，提供有本文教示方法而獲得 之高度交聯聚丙烯材料。 本發明之特別態樣提供一種高度交聯聚丙烯材料，其 包括由複數個重複結構單元形成的複數個聚合物鏈，其中 聚丙烯材料包括：每6個結構單元中具有至少一個碳-碳雙 鍵’及/或聯結（link)相鄰鏈的碳-碳雙鍵。 高度交聯電漿聚丙烯材料可具有任何一種或多種之下 列特性：楊氏模數超過1.5GPa、硬度至少為i〇Mpa，以及 k值在1. 5與2. 6之間。 根據本發明之另一態樣，提供有一種本文教示方法而 獲得之包含高度交聯聚丙烯材料層之基板。 本發明之另一態樣提供一種積體電路，其包含：由本 文教示方法而獲得之高度交聯聚丙烯材料所形成之至少一 介電層。 本文教示的方法可以製造具有介電常數較低之高度交 聯聚丙烯材料，例如以層之形式。再者，聚丙烯中形成的 三雉交聯確保此材料或層相當地熱穩定，以及進—步確保 其在Ashby之後展現出與陶瓷相當的機械性質。pEcvD製 造層並不依靠溶劑或水。教示方法製造的層所生成的一致 性、熱穩定性及低介電常數，使其相當適合在積體電路的 製造中當介電層使用。有益的是，本發明提供單一製程步 驟來產生聚丙烯聚合物鏈及其之間的交聯，而且不需要額 94932 10 201136949 外的固化步驟來提供這些交聯。 , 在較低壓力下，交聯聚丙烯在基板上形成連續層。根 據較佳方法，選用低於5 T〇rr的壓力，以在基板上產生所 需的連續層。在其他較佳方法中，尤其是所需交聯聚丙烯 為形成於電漿相中的薄片狀或奈米粒子（nano-particles) 時’則選用大於5 Torr的壓力。 聚两婦層的機械應力通常與壓力成反比，係因為基板 上的離子撞擊能量較大。離子撞擊為電漿形成製程本身的 一部份’在其他考量中’可以用耦合於電漿的電源、壓力 以及電極的組態加以控制。本技術領域中具有通常知識者 可以經由其他製程進行離子撞擊。在其他情況中，離子撞 擊影響層對基板的黏著性以及表面能量。因此，在較佳實 ^例中，腔體中的壓力則選用大於200 mTorr。 交聯聚丙烯層中的應力亦為施加於電漿電極上每單位 面積的功率作用。施加功率越大，交聯聚丙烯層生長速率 就越快，但層的機械應力也越大。因此，在較佳實施例中， 電滎·電極每單位面積所施加的功率低於0.25 Watts/cm2。 更佳者’電極每單位面積所施加的功率低於〇. 1 Watts/cm2。 機械應力可隨電極上每單位面積施加功率而進一步地降 低。 較佳者，當控制層之離子撞擊以形成聚丙烯層時，將 電襞及偏壓條件設計成對聚丙烯層的傷害最小。因此，基 被可電性接地以製造高品質的薄膜。 聚合物材料中的1¾度三維交聯提供比習知聚丙炸還尚 if! Π 94932 201136949 的溶點。此交聯可 > 」以在結構所有的三維空間中延伸。據此 取H 材料能使用於廣大範圍的用途。此外，此 s材料有助於將潛變極小化以及增強機械性質。 相較於習知採用二氧化石夕作為介電層的積體電路，本 文在此教不的聚丙烯層種類所提供的積體電路，還能更有 效率地操作。此係因為在此教示的交聯聚丙烯層的介電常 數或k值遠低於二氧化矽的介電常數。如此降低了層中儲 存的能量，並對應地降低了干擾’藉以允許切換時間更加 快。 在進一步實施例中’能具有二層或更多層的介電堆 疊，在其之上，所述的聚丙烯層與標準二氧化矽或氮化矽 層的夾心結構結合，或者，包含於標準二氧化矽或氮化矽 層的夾心結構中。 根據本發明之另一態樣，提供有一種製造高度交聯聚 丙烯材料之方法，其包含下列步驟：提供一反應腔室；饋 入一種或多種經選擇的含碳氣體至該腔室，該含碳氣體不 包含丙烯；在該腔室中撞擊電漿，該電漿使該氣體或該等 氣體游離成包含曱基自由基的相；使該游離相形成核並藉 以產生高度交聯聚丙烯材料。 本發明的此態樣可以使用本文在此教示的任何較佳之 特徵，包含依附或相關於申請專利範圍第1項的附屬項中 之任一項或各自項所陳述者。 【貫施方式】 參見第1圖，用於電漿增益化學氣相沉積（PECVD)之裝 12 94932 201136949 置1包括腔室（chamber)2，腔室2容納失盤（chunk)3，夾 盤3上安裝有基板4。在本實施例中，基板4由矽形成。 但是，可用其他材料作為基板。舉例來說，可使用如錯之 半導體材料。或者’也能使用金屬。 在腔室的頂部為噴灑頭5,其功用在於當作氣體入口 以及電漿電極。更具體地說，噴灑頭5具有入口（inlet)6 以及數個出口（outlet)7，噴灑頭5經過入口 6接收PECVD 製程用的原料（feedstock)氣體，原料氣體可經由出口 7排 出喷麗頭5並進入腔室2。喷麵5較佳為金屬。雖然喷 灑頭5在本實施例中的功用為#作電極，但可使用額外或 替換性的電極結構。 設置電源供應器8可施加電壓至喷灑頭5。在較佳實 施例中，電源供絲8提供13.56MHz左右頻率的交流電 (AC)。雖錄佳為至少1Hz，但也可以用料頻率。然而， 在其他實施例中’電源供應器8可提供不同頻率的AC或可 使用直流電⑽M錄如此，AG為較佳者，因為其消除了 在電極間累積電荷的風險’並因此允許電漿在較低功率位 準（level)下進行撞擊。切換式電源或線㈣制雙極電源可 耗口至電漿以游離氣體，以及極小化離子撞擊。限制電源 供應器8提供的電源以防止其他離子撞擊造成對沉積層的 傷害。 腔至2的底部為氣體出口 9,可用真空幫浦（pump)10 將腔室2中的氣體經過氣體出口 9排出。在本實施例中， 真空幫浦1G為加逮分子幫浦（turbo m〇lecular p_)。在 13 94932 ^ 201136949 另一實施例中，真空幫浦10為旋轉幫浦（rotary pump)。 真空幫浦10可將腔室2中的壓力減至如5xl(r7(5e_7)Torr 左右一般低的程度。 也設置有乙炔（C2H2)供應室11。替換乙快的含碳氣體 亦可使用。.乙炔供應室11將乙炔氣體提供至腔室中’其速 率由質量流控制器12所控制。可包含過濾器13以過濾來 自乙炔供應室11的乙炔的供應。亦有設置補充氣體供應室 14。補充氣體供應室14提供補充氣體’該補充氣體經由質 量流控制器12也傳輸至腔室中。若有需要，也設置有進一 步的補充氣體供應室（未圖示）布置來供應補充氣體至腔室 2。質量流控制器12藉此能調節乙炔氣體以及腔室2中補 充氣體或多種氣體的相對比例。供應至腔室2中的乙炔氣 體與補充氣體或多種氣體的組合即稱為原料氣體。原料氣 體可包含乙炔與丙酮的組合。 在較佳實施例中，補充氣體為氫氣，儘管可使用替換 性或額外的補充氣體。乙炔供應室丨丨通常為加壓且包含多 孔性材料。乙炔氣體儲存在多孔性材料内的液態丙明 (CHaCOCHO中。丙_為揮發性碳氫化合物，而且通常發現為 由乙炔供應室11供應的氣體，因此較佳者為非純乙^而為 乙炔與丙_組合。在-些實施例中，較佳者為確保原料 氣體維持至少一定比例的丙嗣’以改善下列所述之胖平 丙烯材料的製造。 外 在本實施例中的質量流控制器12布置來提供含 比例兩__料氣^根據需要，—的比财以為任意 94932 14 201136949 值仁在較佳實施例中為介於〇. 1%與之間。示範原料 ，體包括5%丙酮與95%氫氣。氫氣成份可由惰性氣體(例如 乱乳）或If性以及還原性氣體混合物（例如1氣與氮氣）所 取代。可由5%的乙炔與_組合所取代。 為了用PECVD裝置i來沉積材料於基板4上，先用真 工幫浦1G將腔室2抽真空。接著將原料氣體從乙炔供應室 11以及補充氣體供應室14經由質量流控㈣12饋入腔室 2 ^從此點觀之，真空幫浦1〇係用來維持腔室2中的固 定麼力。轉力的調節可藉由腔室與真空幫浦間之可調闊 的使用、或氣體流速調節來達成。在較佳實施例 中C力調即成2〇〇 mTorr以上。在較低的壓力下，在基 板4上的離子撞擊能量較高，且會對聚丙稀層造成傷害， 而在特㈣作條件下會進—步導致錢不穩定。 當原料氣體位於腔室2中時，電源供應器器8提供ac 或DC至喷麗頭5以撞擊電漿於腔室2中。電聚接著維持在 2狀態，而且產生PECVD製程。結果，高度交聯聚丙烯 j膜冰積在基板上。能提供加熱器（未圖示）以施加額外的 …至基板以增加交《丙_膜的熱穩定性。在較佳 =中’加熱器用於⑽。U刚代之間，較佳為鮮^ 〇C之間，而且最佳為25n^ 之間的溫度下施加 熟。在此製程期間可使用uv電漿撞擊。 交聯聚丙烯形成的機制係因腔室2中的壓力而異。 操作條件在略高於5Torr的壓力下聯： 細在«中生成，接著沉積在基板上。在略低於5—的. 94932 15 201136949 壓力下，高度交聯聚丙烯直接生成在基板4本身上。兩種 製程間的差異影響到交聯聚丙缚薄膜或材料的性質。 在略高於5 Torr下，高度交聯聚丙烯在電漿相（phase) 中形成核，並且包括一起沉積以形成層於基板4上的數種 不同粒子。結果，在層中有數區域留下空白，且不論層處 在何種大氣壓（atmosphere)都會出現。從有效k_值方面來 看，此為有助益的效應，因為空氣的k值非常低（趨近於 1)。然而，在電漿相中形成核的材料不會提供平滑的上表 面以幫助附加層的鍵結。如果需要的話，後處理可將層平 坦化以產生非常平滑的表面，用於整合至裝置結構，或者， 可允許用適合的環氧樹脂混合，使薄膜得以產生。 在略低於5 Torr的壓力下，交聯材料直接在基板4上 成核。其物理性質不同，特別是因為其在基板4上以平滑 表面形成連續層。Chawla discloses a method for forming a plasma polymerized polypropylene film on a substrate in which a propylene monomer is polymerized in a radio frequency plasma reactor at a low pressure. Due to the energy coupling from the plasma, it is expected that polypropylene will be formed via polymerization of propylene. Other prior art that has been disclosed in the prior art are U.S. Patent Nos. 4,632,844, 4,312,575 and US 5,083. SUMMARY OF THE INVENTION The present invention seeks to provide a method and apparatus for making highly crosslinked polypropylene-like materials, such as electronic circuits and optoelectronic circuits comprising such materials. According to an aspect of the present invention, there is provided a method of producing a highly crosslinked polypropylene material comprising the steps of: providing a reaction chamber; selecting one or more carbonaceous gases from a plurality of carbonaceous gases; and one or more The selected carbonaceous gas is fed into the chamber; the plasma is impinged in the chamber, and the plasma dissociates the gas or gases into a methyl radical 2 phase; causing the free phase to form a core and thereby The production of highly crosslinked polypropylene materials is preferably carried out under high UV light shots. Advantageously, the polypropylene material comprises a plurality of repeating structural unit polymer chains' having an average of at least one crosslink per 6 structural units, and/or a plurality of crosslinks spanning adjacent polymer chains. It has been found that the polypropylene 6 94932 201136949 olefin material produced by the present method exhibits significantly improved properties, including extremely low dielectric constant, good structural properties and high melting point, and enhanced mechanical stability compared to conventional polypropylene. . This feature makes this material suitable for a wide variety of applications, including dielectric or insulating layers for integrating electronic or optoelectronic circuits. It is also suitable for a wide variety of other applications, such as providing protection, lubrication, load bearing and/or heat resistant coating. As will be explained below, it is believed that the material produced by this method is a polypropylene-like material. Despite the high degree of influence of three-dimensional cross-linking and improved properties compared to conventional polypropylene, this material exhibits the properties of polypropylene. This material is therefore referred to herein as a polypropylene material, although it is generally understood that this definition encompasses polymeric materials formed by the taught methods and having the properties disclosed herein. Preferably, the one or more selected carbonaceous gas systems are selected from the group consisting of acetylene, acetone, ethylene 'ethanol, methane, and propylene. The best is a combination of acetylene and acetone. In other embodiments, acetylene or acetone alone, or a mixture of acetylene or acetone with any other gas may be used. In this regard, it has been found that highly three-dimensionally crosslinked polypropylene materials can be produced without the use of propylene as a starting material. Other carbon-containing gases or vapors (vapour) can be used. In other words, this method can be used to select one or more carbon-free gases that do not contain polypropylene. The polypropylene material produced from any of the various carbon-containing gases has been found to be the result of the carbon-containing input gas in the methyl radical-containing phase being detached by the plasma impact. This method provides for the fusion of these methyl radicals with CH chain molecules and forms a highly crosslinked polypropylene material. 7 94933⁄4 201136949 uv radiation is provided in this process to promote and enhance 3D cross-linking. This feature helps to allow a greater variety of input materials to be used in the process, so the input material can be selected based on the desired characteristics of the process and the final product. The input gas may contain a gas such as acetone. It should therefore be understood that the gas referred to herein also contains vapor. In the case of the rut, the plasma has an ultraviolet radiation line that enhances the production of cross-linking in the polypropylene material. The ultraviolet light-ray component beneficially has the effect of UV-curing the polypropylene material during the synthesis of the polypropylene material. In actual practice, the method includes the steps of "providing 帛_ and the second electrical electrode, wherein the nucleation step comprises applying a potential difference between the first and second electrodes. In an embodiment, the method provides a substrate disposed on the first and second electrodes. The nucleation step includes applying a potential difference between the first and second electrodes to deposit a nucleating material on the electrode whereby a layer of highly crosslinked polypropylene material is formed on the substrate. Thus, in this embodiment, the polypropylene material is formed directly on the device table. The substrate may be an I5 wound of an electrical or electronic circuit. The π degree and polyacrylic material provide an electrically insulating layer on the substrate. In other words, this feature directly forms a dielectric layer on the electronic device, and the layer exhibits Particularly advantageous characteristics as taught herein. In another embodiment, the polyacrylic material can be in the form of particles or flakes in the electropolymer phase, the core, which can be described as "snowflake (s_), Generally grown in this embodiment, the method advantageously comprises the steps of: collecting the polypropylene material 'and subsequently depositing the material on the substrate (four). It can suspend or dissolve poly 94932 8 201136949 material in solution. This suspended or dissolved material can then be deposited on the substrate by spray coating, spin coating, electrostatic coating or any other suitable method. Preferably, the method comprises providing a carrier gas comprising at least one make-up gas in the chamber. The make-up gas advantageously comprises one or more of the following: hydrogen, nitrogen, helium, argon, helium or other noble gas. The make-up gas promotes the gas component to be free in the plasma to create a layer (e.g., film), flake or particle form of the crosslinked polypropylene material. A high ionization potential can also be exhibited relative to the carbonaceous gas selected for free use. In other words, when one raises the relative amount of all plasma energy and the free species involved in the growth of the polymer layer in the plasma, one or more make-up gases can help ensure that the carbon-containing gas can ionize at relatively low energy. Preferably, the material is also annealed. Annealing has been found to alter or reduce the dielectric constant of the polypropylene material. In fact, it is preferred that the annealing step be carried out in a vacuum or gas controlled environment using a gas controlled environment such as one of inert gases or a combination of inert gases. Beneficially, the method comprises the steps of: providing additional heating in the chamber by non-plasma during the plasma nucleation or synthesis step. The actual embodiment includes the steps of: providing a substrate in the chamber, wherein the substrate is in contact with the electrode; impacting the plasma in the chamber by applying a voltage to a counter electrode in the chamber, thereby The fc_L forms a layer of material in which the plasma has an ultraviolet radiation component that enhances the cross-linking of the polymer in a two-dimensional space by 9 94932 201136949 to impart mechanical integrity and thermal stability to the formed material. According to another aspect of the invention, a highly crosslinked polypropylene material obtained by the teachings herein is provided. A particular aspect of the invention provides a highly crosslinked polypropylene material comprising a plurality of polymer chains formed from a plurality of repeating structural units, wherein the polypropylene material comprises: at least one carbon-carbon double in every six structural units The bond 'and/or the carbon-carbon double bond of the adjacent chain. 5之间之间。 The high-cross-linking plasma polypropylene material may have any one or more of the following characteristics: a Young's modulus of more than 1.5 GPa, a hardness of at least i 〇 Mpa, and a k value between 1.5 and 2.6. According to another aspect of the invention, there is provided a substrate comprising a layer of highly crosslinked polypropylene material obtained by the teachings herein. Another aspect of the present invention provides an integrated circuit comprising: at least one dielectric layer formed of a highly crosslinked polypropylene material obtained by the teachings herein. The methods taught herein can produce highly crosslinked polypropylene materials having a low dielectric constant, such as in the form of a layer. Furthermore, the triterpene crosslinks formed in the polypropylene ensure that the material or layer is relatively thermally stable and further ensure that it exhibits mechanical properties comparable to ceramics after Ashby. The pEcvD fabrication layer does not rely on solvents or water. The uniformity, thermal stability, and low dielectric constant generated by the layers produced by the teaching method make it quite suitable for use as a dielectric layer in the fabrication of integrated circuits. Beneficially, the present invention provides a single processing step to produce polypropylene polymer chains and cross-linking therebetween, and does not require a curing step other than 94932 10 201136949 to provide these crosslinks. At lower pressures, the crosslinked polypropylene forms a continuous layer on the substrate. According to a preferred method, a pressure of less than 5 T rr is selected to produce the desired continuous layer on the substrate. In other preferred methods, especially when the desired crosslinked polypropylene is in the form of flaky or nano-particles formed in the plasma phase, a pressure greater than 5 Torr is selected. The mechanical stress of the two layers is usually inversely proportional to the pressure because the ion impact energy on the substrate is large. The ion impingement is part of the plasma forming process itself 'in other considerations' can be controlled by the configuration of the power source, pressure, and electrodes coupled to the plasma. Those skilled in the art can perform ion strikes via other processes. In other cases, the ion impact affects the adhesion of the layer to the substrate as well as the surface energy. Therefore, in the preferred embodiment, the pressure in the chamber is selected to be greater than 200 mTorr. The stress in the crosslinked polypropylene layer is also the power applied per unit area applied to the plasma electrode. The higher the applied power, the faster the growth rate of the crosslinked polypropylene layer, but the greater the mechanical stress of the layer. Therefore, in the preferred embodiment, the power applied per unit area of the electrode/electrode is less than 0.25 Watts/cm2. More preferably, the power applied per unit area of the electrode is less than 0.1 Watts/cm2. Mechanical stress can be further reduced as power is applied per unit area on the electrode. Preferably, when the ions of the control layer strike to form the polypropylene layer, the electrical and bias conditions are designed to minimize damage to the polypropylene layer. Therefore, the substrate is electrically grounded to produce a high quality film. The 13⁄4 degree three-dimensional cross-linking in the polymer material provides a melting point than the conventional poly-propanoid frying if! Π 94932 201136949. This cross-linking can > "extend in all three-dimensional spaces of the structure. Accordingly, the H material can be used for a wide range of applications. In addition, this s material helps to minimize potential changes and enhance mechanical properties. The integrated circuit provided by the type of polypropylene layer taught herein cannot be operated more efficiently than the conventional integrated circuit using the same as the dielectric layer. This is because the dielectric constant or k value of the crosslinked polypropylene layer taught herein is much lower than the dielectric constant of cerium oxide. This reduces the energy stored in the layer and correspondingly reduces the interference 'by allowing the switching time to be faster. In a further embodiment, a dielectric stack capable of having two or more layers, on which the polypropylene layer is combined with a sandwich structure of a standard ceria or tantalum nitride layer, or included in a standard In the sandwich structure of the ruthenium dioxide or tantalum nitride layer. According to another aspect of the present invention, there is provided a method of making a highly crosslinked polypropylene material comprising the steps of: providing a reaction chamber; feeding one or more selected carbonaceous gases to the chamber, The carbon-containing gas does not contain propylene; it impinges on the plasma in the chamber, the plasma frees the gas or the gases into a phase containing a sulfhydryl radical; forming the free phase to form a core and thereby producing a highly crosslinked polypropylene material. This aspect of the invention may be made using any of the preferred features taught herein, including any one of the dependent items or dependent items in the dependent claims. [Practical mode] See Figure 1 for plasma gain chemical vapor deposition (PECVD). 12 94932 201136949 1 includes chamber 2, chamber 2 contains chunk 3, chuck The substrate 4 is mounted on 3. In the present embodiment, the substrate 4 is formed of tantalum. However, other materials may be used as the substrate. For example, a semiconductor material such as the wrong one can be used. Or 'metal can also be used. At the top of the chamber is a sprinkler head 5 which functions as a gas inlet and a plasma electrode. More specifically, the sprinkler head 5 has an inlet 6 and a plurality of outlets 7, through which the sprinkler head 5 receives a feedstock gas for a PECVD process, and the material gas can be discharged through the outlet 7 5 and enter the chamber 2. The spray surface 5 is preferably metal. Although the function of the shower head 5 in this embodiment is #electrode, an additional or alternative electrode structure may be used. The power supply 8 is set to apply a voltage to the shower head 5. In the preferred embodiment, power supply wire 8 provides alternating current (AC) at a frequency of about 13.56 MHz. Although the recording is preferably at least 1 Hz, the material frequency can also be used. However, in other embodiments 'power supply 8 may provide AC at different frequencies or may use direct current (10) M to record as such, AG is preferred because it eliminates the risk of accumulating charge between electrodes' and thus allows plasma to The impact is made at a lower power level. The switched-mode power supply or line (4) bipolar power supply can drain the plasma to free gas and minimize ion impact. The power supplied by the power supply 8 is limited to prevent other ions from colliding to cause damage to the deposited layer. The bottom of the chamber to 2 is a gas outlet 9, and the gas in the chamber 2 can be discharged through the gas outlet 9 by a vacuum pump 10. In the present embodiment, the vacuum pump 1G is a turbo pump (turbo m〇lecular p_). In another embodiment, 13 94932 ^ 201136949, the vacuum pump 10 is a rotary pump. The vacuum pump 10 can reduce the pressure in the chamber 2 to a level as low as about 5xl (r7 (5e_7) Torr. Also, an acetylene (C2H2) supply chamber 11 is provided. A carbon-containing gas that replaces B can also be used. The acetylene supply chamber 11 supplies acetylene gas into the chamber 'the rate of which is controlled by the mass flow controller 12. A filter 13 may be included to filter the supply of acetylene from the acetylene supply chamber 11. There is also a supplemental gas supply chamber 14 The make-up gas supply chamber 14 provides a make-up gas that is also transferred to the chamber via the mass flow controller 12. If necessary, a further supplemental gas supply chamber (not shown) is also provided to supply the supplemental gas to The chamber 2. The mass flow controller 12 can thereby adjust the relative proportion of the acetylene gas and the supplemental gas or gases in the chamber 2. The combination of the acetylene gas and the supplemental gas or gases supplied to the chamber 2 is called a raw material. The feed gas may comprise a combination of acetylene and acetone. In a preferred embodiment, the make-up gas is hydrogen, although alternative or additional make-up gases may be used. Pressurized and containing a porous material. Acetylene gas is stored in liquid propionate (CHaCOCHO in a porous material. C- is a volatile hydrocarbon, and is generally found to be a gas supplied from the acetylene supply chamber 11, so it is preferred It is a combination of acetylene and propylene for non-pure E. In some embodiments, it is preferred to ensure that the source gas maintains at least a certain proportion of propylene ketone to improve the manufacture of the fat propylene material described below. The mass flow controller 12 in this embodiment is arranged to provide a ratio of two __ gas to the demand, and the ratio is any 94932 14 201136949 value in the preferred embodiment is between 〇. 1% Demonstration of the raw material, including 5% acetone and 95% hydrogen. The hydrogen component can be replaced by an inert gas (such as milk) or If and a reducing gas mixture (such as 1 gas and nitrogen). 5% acetylene and _ The combination is replaced. In order to deposit the material on the substrate 4 with the PECVD device i, the chamber 2 is first evacuated by the vacuum pump 1G. The raw material gas is then flow-controlled from the acetylene supply chamber 11 and the supplementary gas supply chamber 14 via mass flow control. (four) 12 Into the chamber 2 ^ From this point of view, the vacuum pump 1 is used to maintain the fixed force in the chamber 2. The adjustment of the rotation force can be achieved by the wide use between the chamber and the vacuum pump, or The gas flow rate adjustment is achieved. In the preferred embodiment, the C force is adjusted to be 2 〇〇 mTorr or more. At a lower pressure, the ion impact energy on the substrate 4 is higher and the polypropylene layer is damaged. In the case of special (4) conditions, the cost is unstable. When the material gas is located in the chamber 2, the power supply 8 supplies ac or DC to the spray head 5 to strike the plasma in the chamber 2. The electropolymerization was then maintained in the state of 2, and a PECVD process was produced. As a result, the highly crosslinked polypropylene film was ice-formed on the substrate. A heater (not shown) can be provided to apply additional ... to the substrate to increase the thermal stability of the propylene film. In the preferred = medium heater is used for (10). Between the U generations, preferably between the fresh 〇C, and preferably at a temperature of between 25 n^. Uv plasma impact can be used during this process. The mechanism by which the crosslinked polypropylene is formed varies depending on the pressure in the chamber 2. The operating conditions are linked at a pressure slightly above 5 Torr: finely formed in « and then deposited on the substrate. The highly crosslinked polypropylene is directly formed on the substrate 4 itself under a pressure slightly lower than 5 - 94932 15 201136949. The difference between the two processes affects the properties of the cross-linked polypropylene film or material. At slightly above 5 Torr, the highly crosslinked polypropylene forms a core in the plasma phase and includes several different particles deposited together to form a layer on the substrate 4. As a result, a number of areas in the layer leave a blank and appear regardless of the atmospheric pressure at which the layer is located. From the perspective of effective k_values, this is a helpful effect because the k value of air is very low (close to 1). However, the material that forms the core in the plasma phase does not provide a smooth upper surface to aid in the bonding of the additional layers. If desired, the post treatment can flatten the layer to produce a very smooth surface for integration into the device structure, or it can allow for the film to be produced by mixing with a suitable epoxy resin. The crosslinked material nucleates directly on the substrate 4 at a pressure slightly lower than 5 Torr. Its physical properties are different, in particular because it forms a continuous layer on the substrate 4 with a smooth surface.
第2A及2B圖所示為電漿相中的成核材料（以下稱“材 料A”）以及基板上的成核材料（以下稱“材料^，）之光譜 201、204，其係從傅立葉轉換紅外線光譜儀（FTIR spectroscopy )裝置獲得。習知製造之聚丙烯之對照樣本之 光譜202，也有列示出來。 從第2A及2B圖可見’在高於5T〇rr壓力下生成的材 料A 201以及在低於5 Torr壓力下沉積的材料B 2〇4，與 聚丙烯的對照樣本202共享有數個吸收峰值。可據此推 測，材料A及B皆具有類聚丙烯骨幹結構（意即，它們包含 了聚丙烯聚合物鏈）。然而，材料A及B的光譜2〇1、2〇4 94932 16 201136949 的額外峰值顯示了它們與標準聚丙烯2〇2不同。尤其是， 材料Λ及B的光譜201、204皆顯示與c=c雙鍵（〇ie〇phinic 鍵）有關的蜂值。此鍵係有關於交聯聚合物鏈，其增多的交 聯具有提升材料的溫度穩定性的巨觀效果，而且也提供: 些機械性優點’例如低潛變及增強的機械完整性 (integrity) ° 能ϊ在電衆中幫助製造聚合物鏈之間的交聯。此能量 通常包含紫外光輻射’雖然其可“其他形式釋放。舉例 來說’使用含電漿的紫外光輕射可以有效地提供複合型單 —聚合物（combined singular P〇lymer)的製造以及固化製 程步驟’幫助直接製造具有優良的巨觀性f的交聯聚丙稀 層。電I具有紫外光成f分，而且，較佳者亦具有較高能量 電漿種類、離子以及電子。 第3圖繪示.習知聚丙烯聚合物鏈的結構單元的建構區 塊（building block)。此單元為重複的，以提供線性聚合 物鏈。交聯為線性鏈彼此連接的點。 分析第2A及2B圖中材料A及B的光譜2〇1、204，允 許估算相對於結構單元的數目之在材料中C=c鍵的數目。 第2A圖也顯示聚醋的光譜203,其用於估算各種鍵在ρτ IR 光譜儀中的峰值截面積（peak cross section)。經計算鍵 的相關截面積，藉由比較SP2C-H及〇=C鍵在其光譜201、 204中的峰值比例能估算出材料A及B的每一結構單元的 c=c鍵的數目。 使用上述分析後，發現材料八及B平均而言表現出每 94932 17 201136949 6個聚合物鏈單元中有至少一個C=C鍵。在較佳實施例中， 此比例可能提高至每4個單元中有一個OC鍵。C=C鍵係 歸因於聚合物鏈之間的交聯。在此等聚合物鏈中，如此為 高度交聯，並提供了巨觀優點，包含優越的熱穩定性以及 可忽略的潛變。 第3圖中繪示的單一結構單元已知稱為丙烯 (propylene)，或者，更常稱為丙烯（propene)。交聯的比 率藉以定義出相對於鏈中丙烯單元的數目之交聯的數目。 用PECVD方法製造的高度交聯聚丙烯，表現出比習知聚丙 烯更佳的熱穩定性。更明確的說，習知聚丙烯的熔點約在 160°C左右，而高度交聯聚合物的熔點為至少300°C。在較 佳實施例中，熔點甚至還可能更高。舉例來說，在其PECVD 合成期間加熱高度交聯聚丙烯材料進一步提高了其熔點， 就如同隨後的退火一樣。UV電漿撞擊及退火的結合可以用 來進一步提升材料性質以及聚丙烯的交聯。較佳者，高度 交聯聚丙烯的熔點為至少350°C。 第4A及4B圖分別繪示了材料A及B的熱穩定性。此 材料於溫度範圍下在真空中退火10分鐘後，接著分析退火 結果的FTIR光譜。習知製造之聚丙烯之對照樣本之光譜 202也顯示於第4A及4B圖中。Figures 2A and 2B show the nucleation material in the plasma phase (hereinafter referred to as "material A") and the spectra 201, 204 of the nucleation material (hereinafter referred to as "material ^," on the substrate, which are converted from Fourier. A FTIR spectroscopy apparatus is available. The spectrum 202 of a control sample of a conventionally produced polypropylene is also shown. From Figures 2A and 2B, it can be seen that the material A 201 produced at a pressure higher than 5T 〇rr and The material B 2〇4 deposited under a pressure lower than 5 Torr shares several absorption peaks with the control sample 202 of the polypropylene. It can be assumed that both materials A and B have a polypropylene-like backbone structure (that is, they contain poly The propylene polymer chain). However, the extra peaks of the spectra of materials A and B 2〇1, 2〇4 94932 16 201136949 show that they are different from the standard polypropylene 2〇2. In particular, the spectrum of the material Λ and B201, 204 shows the bee value associated with the c=c double bond (〇ie〇phinic key). This bond is related to the crosslinked polymer chain, and the increased cross-linking has a giant effect of improving the temperature stability of the material, and Also available: Some mechanical advantages' The low creep and enhanced mechanical integrity (integrity) ° ϊ can help crosslinking between polymer chains in the manufactured electrical congregation. This energy typically contains ultraviolet radiation ', although it can be "other forms released. For example, 'Using a plasma-containing UV light shot can effectively provide a composite singular Pylymer manufacturing and curing process step' to help directly produce crosslinks with excellent macroscopicity f Polypropylene layer. The electric I has an ultraviolet light of f, and preferably has a higher energy plasma type, ions, and electrons. Figure 3 is a diagram showing the construction block of a structural unit of a conventional polypropylene polymer chain. This unit is repeated to provide a linear polymer chain. Crosslinking is a point at which linear chains are connected to each other. The spectra 2〇1, 204 of materials A and B in Figures 2A and 2B are analyzed, allowing the number of C=c bonds in the material to be estimated relative to the number of structural units. Figure 2A also shows a spectrum 203 of the polyacetate used to estimate the peak cross section of the various bonds in the ρτ IR spectrometer. By calculating the relevant cross-sectional area of the bond, the number of c=c bonds for each structural unit of materials A and B can be estimated by comparing the peak ratios of SP2C-H and 〇=C bonds in their spectra 201, 204. Using the above analysis, it was found that materials VIII and B exhibited, on average, at least one C=C bond per 6 of the 94,932,136,369,949 polymer chain units. In a preferred embodiment, this ratio may be increased to one OC bond per 4 cells. The C=C bond is attributed to cross-linking between polymer chains. In such polymer chains, this is highly crosslinked and offers great advantages, including superior thermal stability and negligible creep. The single structural unit depicted in Figure 3 is known as propylene or, more commonly, propene. The ratio of cross-linking is used to define the number of crosslinks relative to the number of propylene units in the chain. The highly crosslinked polypropylene produced by the PECVD method exhibits better thermal stability than conventional polypropylene. More specifically, conventional polypropylene has a melting point of about 160 ° C and a highly crosslinked polymer has a melting point of at least 300 ° C. In a preferred embodiment, the melting point may even be higher. For example, heating a highly crosslinked polypropylene material during its PECVD synthesis further increases its melting point, just like subsequent annealing. The combination of UV plasma impingement and annealing can be used to further enhance material properties and cross-linking of polypropylene. Preferably, the highly crosslinked polypropylene has a melting point of at least 350 °C. Figures 4A and 4B show the thermal stability of materials A and B, respectively. After annealing the material for 10 minutes in a vacuum at a temperature range, the FTIR spectrum of the annealing result was analyzed. A spectrum 202 of a control sample of a conventionally produced polypropylene is also shown in Figures 4A and 4B.
第4A圖中顯示的材料A光譜說明了即使在1000°C下 退火後，此材料仍保留其結構。並說明即使在這種溫度下， 特徵吸收帶（absorption band)也保存了下來。同樣地，第 4B圖中所示的材料B光譜說明了在退火溫度高達400°C 18 94932 201136949 下，此材料保留了其結構。 觀察到材料A及B光譜中的吸收帶相對強度不同，係 為不同溫度下退火的結果。至少有部份可將此歸因於提供 交聯的聚合物鏈之間的鍵有變化。更明確的說，已推論出 退火造成C=C雙鍵被芳香鍵取代。芳香鍵包括碳原子共輛 環，並展現較高的穩定性。一般而言，在芳香鍵中有6個 碳原子。在退火溫度高於750°C下，C=C雙鍵完全被芳香鍵 所取代。 對此等高溫下的聚合物而言，高度交聯聚丙烯的穩定 性為不平常的。結果，此材料能在較廣種類條件下使用而 不劣化。此乃歸功於在聚合物鏈之間的高度三維交聯。 雖然經過高溫退火後材料A及B的整體結構保持完 整，如第4A及4B圖中所示，但材料的巨觀性質可能發生 變化。當材料隨後進行加熱時，可以用退火製程來熱‘硬 化’材料，以限制巨觀的改變。額外的退火步驟較佳在至 少100°C，更佳為至少200°C，而且最佳為至少300°C的溫 度下進行。 正如同相對習知聚丙烯加強的熱穩定性，高度交聯聚 丙烯已提升機械性質，尤其是楊氏模數（Young’s modulus) 超過1. 5 GPa，而且硬度至少為1 OMPa。此外，高度交聯材 料表現出可忽略的潛變、增強的機械性質，因此更接近地 相似於工業陶瓷。 如此支持了以下結論：在材料中的C=C雙鍵係歸因於 高度交聯聚合物鏈在減少或防止鏈之間的相對移動的三維 19 94932 201136949 網路或基材（matrix)中。觀察到的極小潛變係因為高度交 聯聚合物鏈相對於標準聚丙烯韌化了生成的材料。 相較於習知聚丙烯’高度交聯聚丙烯的機械與熱性質 令其更適合各種應用，包含：在積體電路製造令，當作層 間介電質（inter-layer dielectric)。尤其是，在電漿相 中形成核的高度交聯材料的k值量測到為1.5左右’在一 實施例中為1.6± G. 5，而且，經由在基板上直接成核形成 的咼度交聯材料的k值量測到為2. 5左右，在一實施例中 為2. 24± 0. 15。這些值可能根據生長條件而調整。 高度交聯聚丙烯材料的k值大幅低於二氧化矽（傳統 上使用在微晶片中作為介電層的物質）的k值（約3.9)。再 者，如第6圖中所繪示，退火係進/步改良高度交聯材料 的k值。退火步驟似乎不會明顯地造成材料減少以及質量 損失’因為如此會反應在厚度的減少以及伴隨增加的k 值。相反地’且驚人地，係觀察到k值的減少。 第5圖繪示了包括交聯聚丙紼封料的電容器裝置。第 7圖繪示了包括交聯聚丙烯材料的積體電路。第8圖繪示 包括交聯聚丙稀材料的替換性積體電路（alternative integrated circuit) ° 須了解的是，本文教示的方法及裝置除了 RF及DC電 衆以外，同樣可以使用感應耗合電聚（ICP )。 本發明揭露的實施例僅作為範例本領域中。具通常技 術及知識者可修改、變化以及改變所揭露的實施例。這些 修改、變化以及改變可在不脫離本發明申請專利範圍及其 20 94932 201136949 等效中定義的範圍内完成。 本申請案主張優先權基礎為英國專利申請案號 0906680. 4,其中的揭露内容以及伴隨此申請案之摘要在此 併入作為參考。 【圖式簡單說明】 本發明的較佳實施例現將藉由僅參考下列圖式的範例 的方式說明，其中： 第1圖繪示電漿增益化學氣相沉積裝置； 第2A圖繪示第一交聯聚丙烯材料的傅立葉轉換紅外 線（FTIR)光譜； 第2B圖繪示第二交聯聚丙烯材料的傅立葉轉換紅外 線（FTIR)光譜； 第3圖繪示聚丙烯聚合物鏈的結構單元； 第4A圖繪示第一交聯聚丙烯材料在FTIR光譜上的退 火效果； 第4B圖繪示第二交聯聚丙烯材料在FTIR光譜上的退 火效果； 第5圖繪示包括交聯聚丙烯材料之電容器裝置； 第6圖繪示交聯聚丙烯材料在k值上之退火效果； 第7圖繪示包括交聯聚丙烯材料之積體電路；以及 第8圖繪示包括交聯聚丙烯材料的替換性積體電路。 【主要元件符號說明】 1 •電漿增益化學氣相沉積裝置 2 腔室 3 夾盤 21 94932 201136949 4 基板 5 喷灑頭 6 入口 7 出口 8 電源供應器 9 氣體出口 10 真空幫浦 11 乙炔供應室 12 質量流控制器 13 過滤器 14 補充氣體供應室 201 光譜 202 光譜 203 光譜 204 光譜 22 94932The material A spectrum shown in Figure 4A illustrates that the material retains its structure even after annealing at 1000 °C. It is also stated that even at this temperature, the characteristic absorption band is preserved. Similarly, the material B spectrum shown in Figure 4B illustrates that this material retains its structure at annealing temperatures up to 400 ° C 18 94932 201136949. The relative intensities of the absorption bands in the materials A and B spectra were observed to be the result of annealing at different temperatures. At least some of this can be attributed to changes in the bonds between the polymer chains providing crosslinks. More specifically, it has been inferred that annealing causes the C=C double bond to be replaced by an aromatic bond. The aromatic bond includes a ring of carbon atoms and exhibits high stability. Generally, there are 6 carbon atoms in the aromatic bond. At an annealing temperature above 750 ° C, the C=C double bond is completely replaced by an aromatic bond. The stability of highly crosslinked polypropylene is unusual for such polymers at elevated temperatures. As a result, the material can be used under a wide variety of conditions without deterioration. This is due to the high degree of three-dimensional cross-linking between the polymer chains. Although the overall structure of materials A and B remains intact after high temperature annealing, as shown in Figures 4A and 4B, the macroscopic properties of the material may vary. When the material is subsequently heated, an annealing process can be used to heat the 'hardened' material to limit macroscopic changes. The additional annealing step is preferably carried out at a temperature of at least 100 ° C, more preferably at least 200 ° C, and most preferably at least 300 ° C. As with the thermal stability of the conventional polypropylene, highly crosslinked polypropylene has improved mechanical properties, especially Young's modulus of more than 1.5 GPa, and a hardness of at least 1 OMPa. In addition, highly crosslinked materials exhibit negligible creep, enhanced mechanical properties and are therefore more similar to industrial ceramics. This supports the conclusion that the C=C double bond in the material is attributed to the three-dimensional 19 94932 201136949 network or matrix in which the highly crosslinked polymer chains reduce or prevent relative movement between the chains. The minimal potential changes observed were due to the highly crosslinked polymer chains toughened the resulting material relative to standard polypropylene. Compared to the mechanical and thermal properties of the conventional polypropylene 'highly crosslinked polypropylene, it is more suitable for various applications, including: in the integrated circuit manufacturing order, as an inter-layer dielectric. In particular, the k value of the highly crosslinked material forming the core in the plasma phase is measured to be about 1.5', which is 1.6 ± G. 5 in one embodiment, and is formed by direct nucleation on the substrate. 5之间。 In the embodiment, the amount of the cross-linking material is 2. 24 ± 0.15. These values may be adjusted depending on the growth conditions. The k value of the highly crosslinked polypropylene material is substantially lower than the k value (about 3.9) of cerium oxide (a material conventionally used as a dielectric layer in a microchip). Further, as depicted in Fig. 6, the annealing is stepwise/stepwise to improve the k value of the highly crosslinked material. The annealing step does not appear to cause significant material reduction and mass loss' because it would react to a decrease in thickness and a concomitant increase in k value. Conversely, and surprisingly, a decrease in the k value is observed. Figure 5 depicts a capacitor device including a cross-linked polypropylene seal. Figure 7 depicts an integrated circuit comprising a crosslinked polypropylene material. Figure 8 illustrates an alternative integrated circuit including a cross-linked polypropylene material. It should be understood that the methods and apparatus taught herein can also use induction-consuming electro-convergence in addition to RF and DC power. (ICP). The disclosed embodiments of the invention are presented by way of example only. The disclosed embodiments may be modified, altered, and altered by those skilled in the art. These modifications, changes and variations can be made without departing from the scope of the invention as defined in the appended claims. The present application claims priority under the U.S. Patent Application Serial No. 0,906, 680, the disclosure of which is incorporated herein by reference. BRIEF DESCRIPTION OF THE DRAWINGS Preferred embodiments of the present invention will now be described by way of example only with reference to the following drawings, wherein: FIG. 1 illustrates a plasma gain chemical vapor deposition apparatus; FIG. 2A illustrates Fourier transform infrared (FTIR) spectrum of a crosslinked polypropylene material; Fig. 2B shows Fourier transform infrared (FTIR) spectrum of the second crosslinked polypropylene material; Fig. 3 shows structural unit of the polypropylene polymer chain; 4A is a graph showing the annealing effect of the first crosslinked polypropylene material on the FTIR spectrum; FIG. 4B is a graph showing the annealing effect of the second crosslinked polypropylene material on the FTIR spectrum; and FIG. 5 is a graph showing the crosslinked polypropylene. Capacitor device of material; Figure 6 shows the annealing effect of the crosslinked polypropylene material on the k value; Fig. 7 shows the integrated circuit including the crosslinked polypropylene material; and Fig. 8 shows the crosslinked polypropylene including An alternative integrated circuit of materials. [Main component symbol description] 1 • Plasma gain chemical vapor deposition device 2 Chamber 3 Chuck 21 94932 201136949 4 Substrate 5 Sprinkler head 6 Inlet 7 Outlet 8 Power supply 9 Gas outlet 10 Vacuum pump 11 Acetylene supply room 12 Mass Flow Controller 13 Filter 14 Supplemental Gas Supply Chamber 201 Spectrum 202 Spectrum 203 Spectrum 204 Spectrum 22 94932