經濟部智慧財產局員工消費合作社印製 1253087Ministry of Economic Affairs, Intellectual Property Bureau, Staff Consumer Cooperative, Printed 1253087
背景 所謂的積體電路（Int d 2_子&_路，縮小並^ 積上的—種電子產品。其技術發展· 疋在較小線見與較大晶片方向來進行的 :能增強並降低製造成本。但是隨著線寬逐漸 連：(lnt:r_ects)所造成的時間延遲將成為影響幻 才呆作速率與性能的最主要因素。 解決上述問題的方法有二，—為降低内連線的電阻 另-為降低介電層的介電常數。在降低介電層介電常數^ 面’常用的方法一為使其具有多孔性的結構(porou structure)，另一為使其增加碳的含量，由此發展出一些^ 有低介電常數之介電材料。而低介電常數材料的形成方月 一般有兩種，一種為旋塗法（spin_〇n)，另一種為化學氣木 沈積法（chemical vapor deposition)。 以旋塗法來說，例如含氫的矽酸鹽類（hydr〇ge] silsesquioxane ; HSQ)，具有多孔性結構，其介電常數約為 2_9。因HSQ容易吸收水氣，結構易受氧電漿破壞。所〇 又發展出含碳量較高之甲基矽酸鹽海 (methylsilsesquioxane ; MSQ)，可以使其介電常數降低至 本紙張尺度適用中國國家標準(CNS)A4規格(210X297公釐)Background The so-called integrated circuit (Int d 2_子 &_路, narrowed down and accumulated on the electronic product. Its technical development 疋 in the smaller line see the direction of the larger wafer: can enhance and Reduce manufacturing costs. But as the line width gradually increases: (lnt:r_ects) caused by the time delay will become the most important factor affecting the speed and performance of the magical. There are two ways to solve the above problems - to reduce the interconnection The resistance of the wire is to reduce the dielectric constant of the dielectric layer. The commonly used method for lowering the dielectric constant of the dielectric layer is to make it porous, and to increase carbon. The content of the dielectric material has a low dielectric constant, and the formation of low dielectric constant materials generally has two types, one is spin coating (spin_〇n) and the other is chemistry. In the case of spin coating, for example, hydrogen-containing hydrazine (silsesquioxane; HSQ) has a porous structure with a dielectric constant of about 2-9. It is easy to absorb water vapor, and the structure is easily damaged by oxygen plasma. Has developed a high carbon content of methyl silicate sea (methylsilsesquioxane; MSQ), it can reduce the dielectric constant to scale this paper applies China National Standard (CNS) A4 size (210X297 mm)
1253087 五 '發明説明（） 約2_7。以化學氣相沈積法來 貝左木也。例如以四甲基矽烷 (tetramehyl Silane)與氧氣反廡 (u , 孔夂應形成之甲基化之氧化矽 Ο-th灿dsil㈣，其介電常數也在27左右。這些對於 〇 · 1微米製程來說，其介電當勤彳 + 书數仍然太高。0.1微米製程 對於"電層之介電常數的要求，最好要到2… 2.5以下。 登目的與 口此本♦明的目的就是在提供_種有機多孔介電材料 之形成方法，以降低積體電路中介電層的介電常數。 /根據本發明之上述目的，提出_種有機多孔介電材料 之形成方法。此方法至少為透過氣體分佈器通入乙稀、環 矽乳烧類化合物與甲基石夕烧類化合物，使其進入電浆反應 區域以沈積有機多孔介電材料於晶圓上。 “ 依照本發明一較佳實施例，環矽氧烷類化合物例如可 為八甲基四石夕氧環烧、四甲基四石夕氧環炫或十甲基五石夕氧 =烷’而甲基矽烷類化合物可為三甲基矽烷或二甲基矽 烧。 由上述可知，利用環矽氧烷類化合物之環狀結構與利 =石夕？類作為環石夕氧烧類化合物分子間之架橋分子，在適 田的％丨兄苓數下，可以在晶圓上形成有機多孔介電材料。 利用此有機多孔材料之多孔性質，可使其介電常 約2.5左右。 本紙張尺度朝巾國目家鮮(CNS)A4絲(2獻297公董） (請先·閱讀背面之注意事項再填寫本頁} -訂- 經濟部智慧財產局員工消費合作社印製 1253087 A7 B7 五、發明説明（ 發明的詳細說明 化學氣相沈積，顧名思義乃是利用化學反應的方式， 使反應物在反應室内反應生成固態的生成物，以在晶圓表 面形成一層薄膜的一種薄膜沈積技術。化學氣相沈積已經 fe然成為半導體製程當中最重要且是最主要的薄膜沈積技 術，因為舉凡所有半導體元件所需之薄膜，不論是導體、半導體或是介電材料，皆可利用化學氣相沈積的技術來沈積之。 一般來說，電漿增強式化學氣相沈積法（plasma e—nCedCVD;PECVD)會在所需之條件（如温度、壓力 專仏件）下將所品之反應物透過氣體分佈器導入至化學 氣相沈積機台之反應室中，然後啟動電浆產生器在_適合 功訂使反應氣體變成電漿（亦即部分離子化的氣體）以 進订化學反應，在晶圓表面沈積出薄膜。在氣體分佈器與 晶圓之間的空間，為產生電漿的區域。在電漿當中，其/、 成有各種帶有電荷的電子與離子，還有不帶電的自由丞 (radical)與原子團，這些都有可能是反應中間物如⑽— 瞻mediate)，再經由適宜的碰撞而產生所需之產物。 二只要控制好電漿產生器的功率，產生所需之反應中 物，就可以順利地進行所需薄膜之沈積。 =此在利用電漿增強式化學氣相沈積法 :::電材料時，若是能利用具有環狀結構之分子與： 木榀之線型分子為反應物，在 ’、、、 電水產生反應中間物’則可在晶圓上沈積出具有低介 組基 所 多 •(請先跹讀背面之注意事項再填寫本頁) 訂· Φ 4 ^張^^中晴標準⑽ΙΓα4規格⑵似297公爱）1 1253087 A7 _______B7 五、發明説明（） 電常數之薄膜。 剛開始選擇環矽氧烷類化合物（如八甲基四石夕氧環 烷，octamethyl cyclotetrasiloxane，縮寫成 〇MCTS，其化 學結構列於下面），與具有不飽和鍵的碳氫小分子化合物 (如乙稀）作為反應物來沈積有機多孔介電材料。發現若兩 者在氣相反應的比例越多，則有機多孔介電薄膜的介電常 數就越低。但是若氣相反應的比例太大時，則因為氣相反 應過於激烈，會形成較大的顆粒落於晶圓上而無法形成均 勻之薄膜或使形成之薄膜内含有較大的顆粒，造成薄膜呈 務狀（haze)。 (請先跹讀背面之注意事項再填寫本頁) h3c、 ch, Si- CHo1253087 Five 'Inventions () about 2_7. It is also chemically vapor deposited to the shell. For example, tetramethylhyl Silane reacts with oxygen (u, methylated yttrium oxide-th-dsil (4) which should be formed by pores, and its dielectric constant is also about 27. These are for the 〇·1 micron process. In fact, the dielectric is diligent + the number of books is still too high. The 0.1 micron process for the dielectric constant of the electrical layer, preferably to 2 ... 2.5 or less. The method for forming an organic porous dielectric material is provided to reduce the dielectric constant of the dielectric layer of the integrated circuit. / According to the above object of the present invention, a method for forming an organic porous dielectric material is proposed. In order to pass through the gas distributor, the ethylene, cyclopentadiene-based compound and the methyl smelting compound are introduced into the plasma reaction region to deposit an organic porous dielectric material on the wafer. "According to the present invention In a preferred embodiment, the cyclodecane compound may be, for example, octamethyltetrazepine, tetramethyltetrasyloxane or decamethylpentaoxane = alkane and the methyl decane compound may be used. It is trimethyl decane or dimethyl hydrazine. As can be seen from the above, the ring structure of the cyclopentane compound and the bridge molecule of the diarrhea compound are used as the bridge molecules of the cyclomethoxazole compound, and the wafer can be used in the wafer. The organic porous dielectric material is formed on the surface. The porous nature of the organic porous material can be made to have a dielectric of about 2.5. The paper scale is toward the national standard (CNS) A4 silk (2 297 dong) (please First, read the notes on the back and fill out this page. - Order - Ministry of Economic Affairs, Intellectual Property Bureau, Staff and Consumers Co., Ltd. Printed 1253087 A7 B7 V. Description of the Invention (Detailed description of the invention Chemical vapor deposition, as the name suggests is the way of using chemical reactions A thin film deposition technique that reacts a reactant in a reaction chamber to form a solid product to form a thin film on the surface of the wafer. Chemical vapor deposition has become the most important and important thin film deposition technique in semiconductor manufacturing. Because all the thin films required for semiconductor components, whether conductors, semiconductors or dielectric materials, can be deposited by chemical vapor deposition techniques. It is said that plasma enhanced chemical vapor deposition (plasma e-nCedCVD; PECVD) will introduce the reactants into the chemical vapor phase through a gas distributor under the required conditions (such as temperature and pressure components). In the reaction chamber of the deposition machine, the plasma generator is then activated to make the reaction gas into a plasma (that is, a partially ionized gas) to customize the chemical reaction, and a film is deposited on the surface of the wafer. The space between the distributor and the wafer is the area where the plasma is generated. Among the plasmas, there are various charged electrons and ions, and uncharged free radicals and atomic groups. It is possible that the reaction intermediates (10) - mediate), and then produce the desired product via a suitable collision. Second, as long as the power of the plasma generator is controlled to produce the desired reaction medium, the deposition of the desired film can be smoothly performed. = When using the plasma-enhanced chemical vapor deposition method:::Electrical material, if it is possible to use a molecule having a cyclic structure and a linear molecule of hibiscus as a reactant, in the middle of the reaction of ',, and electric water 'Things' can be deposited on the wafer with a low dielectric group. (Please read the back of the note and fill out this page) Order · Φ 4 ^ Zhang ^ ^ Zhongqing standard (10) ΙΓ α4 specifications (2) like 297 public ) 1 1253087 A7 _______B7 V. Description of the invention () Film of electric constant. At the beginning, we have selected cyclomethoxane compounds (such as octamethyl cyclotetrasiloxane, abbreviated as 〇MCTS, whose chemical structure is listed below), and hydrocarbon small molecule compounds with unsaturated bonds (such as Ethylene) is used as a reactant to deposit an organic porous dielectric material. It was found that the more the ratio of the two reacted in the gas phase, the lower the dielectric constant of the organic porous dielectric film. However, if the proportion of the gas phase reaction is too large, since the gas phase reaction is too intense, a large particle may be formed on the wafer to form a uniform film or a large particle may be formed in the formed film to cause a film. Haze. (Please read the notes on the back and fill out this page) h3c, ch, Si- CHo
八甲基四矽氧環烷（OMCTS) -訂· Φ 經濟部智慧財產局員工消費合作社印製 亦 應 之 因此必須小心控制氣體分佈器與晶圓之間的距離， 即產生電聚區域的空間大小。若此距離太大，則氣相反 薄膜 在多 (相 =也不易維持穩定的電漿，會沈積出霧狀 '夕，；丨电薄膜。若此距離太小，則有機多孔介 之介電常數又會太高’無法在〇·ι微米製程中使用。4 次試驗之後，氣體分佈器與晶圓之間的距離為950心 本紙張尺度適财關家標準(CNS)A4^ig>< 29 1253087 五、發明説明（） 當於2_41公分，mUs為千分之—英 定電漿的極限了。在此條件下，沈積出：右為維持穩 膜所能達到之最低介電常數約為2 55〜i4、夕孔介電薄 米製程之2.5的要求還有一段距離·。' ·60,距離（M微 為了要增加產生穩定電漿所需環境 (wmdow),必須要尋找更容易離子化之八早、，之足裕度 必須要能作為環矽氧烷類化合物分子間：：：此分子 = 、甲基化合物與環秒氧燒二合物:： U至：2中甲基_員化合物為-甲她、二 物^ 或四甲基㈣，而_氧院類化合 物為八甲基四石夕氧環烧、㈤甲基 氧環烷。 十甲基五矽 以乙烯、甲基石夕烧類化合物與八甲基四石夕氧環垸的及 應結果來說，發現三甲基石夕烧與二甲基錢的結果都不 !::!效果最好的是三甲基石夕烧，因為三甲基石夕统的碳 3里夠夕，而且比四甲基矽烷容易離子化。上述反應中， 以乙烯、三甲基石夕烧與八甲基四石夕氧環燒的反應為例，發 現在加入適量三甲基料的情況下，可將氣體分佈器與^ 圓間的距離拉大至1050 mils (約2 67公分），仍可以在電 漿產生區域維持穩定的電漿。 一般來說，例如當環矽氧烷類化合物之氣體流量約為 2000 - 8000 sccm時，甲基矽烷類化合物之氣體流量可約 為500 — 1000 sccm ，乙烯之氣體流量可約為1〇〇〇 — 2〇〇〇 seem。其他的適合反應條件還有氣體分佈器與晶圓間的較 (請先邮讀背面之注意事項再填寫本頁) -訂_ Φ 經濟部智慧財產局員工消費合作社印製 1253087Octamethyltetraoxaxane (OMCTS) - order · Φ Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing should also be careful to control the distance between the gas distributor and the wafer, that is, the space for generating the electricity gathering area size. If the distance is too large, the gas is opposite to the film (phase = also difficult to maintain a stable plasma, will form a haze); 丨 electric film. If the distance is too small, the dielectric constant of the organic porous It will be too high to be used in the ι·ι micron process. After 4 trials, the distance between the gas distributor and the wafer is 950 cents paper size (CNS) A4^ig>< 29 1253087 V. INSTRUCTIONS () When 2_41 cm, mUs is the limit of a thousand-inch plasma. Under these conditions, the deposition: right is the lowest dielectric constant that can be achieved by maintaining the film. 2 55~i4, the requirements of the 2.5-meter dielectric thin film process 2.5 is still a distance ·. · 60, distance (M micro in order to increase the environment required to produce stable plasma (wmdow), must find easier ion In the early morning, the margin must be able to act as a cyclopentane compound between the molecules::: this molecule =, methyl compound and ring-second oxygenated dimer:: U to: 2 in the methyl group _ The compound is -methyl, di- or tetramethyl (tetra), and the compound of oxygen is octamethyl Burning, (5) methyloxane. Tetramethylpentanium is found in the results of ethylene, methyl sulphide and octamethyltetrazepine oxime. The result of the money is not!!:! The best effect is trimethyl zebra, because the carbon 3 of the trimethyl sulphate is abundant, and it is easier to ionize than tetramethyl decane. In the above reaction, ethylene, trimethyl stone For example, the reaction between Xishao and octamethyltetracycline was found to increase the distance between the gas distributor and the circle to 1050 mils (about 2 67 cm) with the addition of an appropriate amount of trimethylate. ), it is still possible to maintain a stable plasma in the plasma generating region. Generally, for example, when the gas flow rate of the cyclopentane compound is about 2000 - 8000 sccm, the gas flow rate of the methyl decane compound may be about 500. — 1000 sccm, the gas flow rate of ethylene can be about 1〇〇〇-2〇〇〇seem. Other suitable reaction conditions are the ratio between the gas distributor and the wafer (please read the note on the back first and then fill in the form) Page) - set _ Φ Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperation Society Printing 1253087
五、發明説明( 佳距離約為2 - 3 /入公，φ 14变/ / 巧 3 A刀電漿的功率較佳約為600 一 120〇 瓦，反應室内的壓力較佳約為3 _ ^ κ ^ ^ ± 佳為攝氏彻度托耳而反應溫度較 在此知件下形成之有機多孔介電 薄膑’其介電常數可降低至約 千臥王、、/j 2.5左右了，已經可以在〇」 微米製程中使用為介電層的材料。 此外，因為乙烯、甲基石夕燒類化合物與環石夕氧烧類化 合物因其化學結構不同，其產生電漿的適合功率也會有些 差異。因此可利用多個電漿產生器來分別產生乙烯、甲基 矽烷類化合物與環矽氧烷類化合物的電漿之後，再將三者 的電漿導人電漿反應區域來進行化學沈積反應，可以使製 程裕度（process Wind0w)加大。產生環矽氧烷類化合物所需 要之功率通常較乙烯與甲基矽烷類化合物低，只要可以將 分支的化學鍵斷裂即可。 由上述本發明較佳實施例可知，利用環矽氧烷類化合 物之壞狀結構與利用矽烷類作為環矽氧烷類化合物分子間 之架橋分子，在適當的環境參數下，可以在晶圓上形成有 機多孔介電材料。利用此有機多孔材料之多孔性質，可使 其介電常數降低至約2.5左右。 雖然本發明已以一較佳實施例揭露如上，然其並非用 以限定本發明，任何熟習此技藝者，在不脫離本發明之精 神和範圍内，當可作各種之更動與潤飾，因此本發明之保 護範圍當視後附之申請專利範圍所界定者為準。 本紙張尺度適用中國國家標準(CNS)A4規格(210X297公釐) (請先閲讀背面之注意事項再場寫本頁) -訂_ 經濟部智慧財產局員工消費合作社印製Fifth, the invention description (good distance is about 2 - 3 / into the public, φ 14 change / / Qiao 3 A knife plasma power is preferably about 600-120 watts, the pressure in the reaction chamber is preferably about 3 _ ^ κ ^ ^ ± is preferably Celsius and the reaction temperature is lower than that of the organic porous dielectric thin layer formed under the known component. Its dielectric constant can be reduced to about a thousand kings, and /j is about 2.5. In the 微米" micron process, the material used as the dielectric layer is used. In addition, because ethylene, methyl zephyr compound and cyclohexadecene compound have different chemical structures, the suitable power for generating plasma is also somewhat Therefore, a plurality of plasma generators can be used to separately generate plasmas of ethylene, methyl decane compounds and cyclodecane compounds, and then the plasmas of the three are guided to the plasma reaction zone for chemical deposition. The reaction can increase the process margin (process Wind0w). The power required to produce the cyclopentane compound is generally lower than that of the ethylene and methyl decane compound, as long as the chemical bond of the branch can be broken. The preferred embodiment shows that By using the bad structure of the cyclopentane compound and the bridging molecule between the molecules of the cyclodecane compound using decane, an organic porous dielectric material can be formed on the wafer under appropriate environmental parameters. The porous material of the porous material can reduce its dielectric constant to about 2.5. Although the present invention has been disclosed in a preferred embodiment as above, it is not intended to limit the present invention, and anyone skilled in the art can The scope of protection of the present invention is defined by the scope of the appended claims. The paper scale applies to the Chinese National Standard (CNS) A4 specification (210X297). (Limited) (Please read the notes on the back and write this page again) - Order _ Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing