經濟部智慧財產局員工消費合作社印製 580523 A7 __B7 五、發明說明（） 發明領域 本發明是有關於一種化學氣相沈積的方法，且特別是 有關於一種以雙電漿源來進行化學氣相沈積的方法。 發明背景 化學氣相沈積，顧名思義乃是利用化學反應的方式， 使反應物在反應室內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 儼然成爲半導體製程當中最重要且是最主要的薄膜沈積技 術’因爲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’會在所需之條件(如溫度、壓力等條件)下， 將所需之反應物導入至化學氣相沈積機台之反應室中，然 後啓動電漿產生器使反應氣體變成電漿（亦即部分離子化 的氣體）以進行化學反應，在晶圓表面沈積出薄膜。在電 漿當中，其組成有各種帶有電荷的電子與離子，還有不帶 電的自由基（radical)與原子團，這些都有可能是反應中間 物（reaction intermediate)，再經由適宜的碰撞而產生所需 之產物。所以只要控制好電漿產生器的功率，產生所需之 反應中間物，就可以順利地進行所需薄膜之沈積。 早期所需之薄膜，其組成與結構都較爲單純，如單純 之金屬鎢、氧化矽或氮化矽薄膜等等，所以可將所需之數 2 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐）Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 580523 A7 __B7 V. INTRODUCTION TO THE INVENTION Field of the Invention The present invention relates to a method for chemical vapor deposition, and more particularly to a method for performing chemical vapor phase with dual plasma sources. Method of deposition. BACKGROUND OF THE INVENTION Chemical vapor deposition, as its name implies, is a thin film deposition technique that uses chemical reactions to make reactants react in a reaction chamber to produce solid products to form a thin film on the surface of a wafer. Chemical vapor deposition has become the most important and most important thin film deposition technology in semiconductor processes. 'Because all the thin films required for semiconductor components, whether it is conductors, semiconductors or dielectric materials, can be used chemical vapor deposition. Technology to deposit it. Generally, 'the required reactants will be introduced into the reaction chamber of the chemical vapor deposition machine under the required conditions (such as temperature, pressure, etc.), and then the plasma generator is started to make the reaction gas into electricity. The slurry (that is, a partially ionized gas) undergoes a chemical reaction to deposit a thin film on the wafer surface. In the plasma, it is composed of various charged electrons and ions, as well as uncharged radicals and atomic groups. These may be reaction intermediates, which are then generated through appropriate collisions. Desired product. Therefore, as long as the power of the plasma generator is controlled to produce the required reaction intermediate, the required film deposition can be smoothly performed. The composition and structure of the films required in the early days are relatively simple, such as pure metal tungsten, silicon oxide, or silicon nitride films, etc., so the required paper size can be adapted to Chinese National Standard (CNS) A4 Specifications (210 X 297 mm)
------ίι.ιιιιφ^--------訂--------- (請先閱讀背面之注意事項再本頁) B 580523 A7 —------- 137 ----------- 五、發明說明（） 種不同反應氣體在適當條件下通入至反應室中，再予 發化進行化學氣相沈積。然而對於目前—些低介電常數之 介電材質來說，因爲其所需之反應物的結構㈣雛1 必須精確地控制反應物的活化程度，以進行選擇性的化與 麵。_浦上述雜賴行__漏，所得之; 月吴材料常無法形成具有低介電常數的材料。 經濟部智慧財產局員工消費合作社印製 發明目的與槪補： 因此本發明的主要目的就是在提供一種化學氣相沈積 的方法’可依不體形]^電_輔需之不同活化 成來分別提供不同的能量，以使不同之反應氣體可分別形 成所需之反應中間物。 根據本發明之上述目的，提出一種以雙電漿源來進行 化學熱相沈積的方法，本方法係使用至少具有二電漿產生 器之化學氣相沈積機台。本方法至少包括通入第一氣體至 第一電漿產生器中，使第一電漿產生器可以第一功率產生 第一電漿。同時，通入第二氣體至第二電漿產生器中，使 第一電獎產生器以第一功率產生第二電槳◦然後，通入第 一電漿與第二電槳至反應室中，以進行化學氣相沈積。 依照本發明一較佳實施例，上述之第一功率不一定要 等於第二功率，第一功率與第二功率主要是依照要使第一 氣體與第二氣體分別產生所需之反應中間物時所需之活化 能而定。第一電漿產生器與第二電漿產生器之位置可依所 3 本紙張尺度適用中國國家標準（CNS)A4規格（21〇 X 297公釐）------ ίι.ιιιιφ ^ -------- Order --------- (Please read the precautions on the back before this page) B 580523 A7 ------- -137 ----------- 5. Description of the invention () Different reaction gases are passed into the reaction chamber under appropriate conditions, and then subjected to chemical vapor deposition. However, for some current low-k dielectric materials, because of the structure of the reactants they require, the degree of activation of the reactants must be precisely controlled in order to perform selective chemical modification. The above mentioned miscellaneous lines are __ leaked, and the resulting materials are often unable to form materials with low dielectric constants. The purpose and supplement of the invention printed by the Consumers 'Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs: Therefore, the main purpose of the present invention is to provide a method of chemical vapor deposition' may vary depending on the shape of the body] ^ electricity _ auxiliary needs are activated separately to provide Different energies, so that different reaction gases can form the required reaction intermediates. According to the above object of the present invention, a method for performing chemical thermal phase deposition using a dual plasma source is proposed. This method uses a chemical vapor deposition machine having at least two plasma generators. The method at least includes passing a first gas into the first plasma generator, so that the first plasma generator can generate the first plasma with the first power. At the same time, the second gas is passed into the second plasma generator, so that the first electricity prize generator generates the second electric paddle with the first power. Then, the first plasma and the second electric paddle are passed into the reaction chamber. For chemical vapor deposition. According to a preferred embodiment of the present invention, the above-mentioned first power does not have to be equal to the second power, and the first power and the second power are mainly according to the time when the first gas and the second gas are required to generate the required reaction intermediates Depending on the required activation energy. The position of the first plasma generator and the second plasma generator can be in accordance with the 3 paper standards applicable to the Chinese National Standard (CNS) A4 specification (21〇 X 297 mm)
580523 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明說明（） 需安置在化學氣相沈積機台上之適當位置，例如第一電獎 產生器可位在反應室之內，而第二電漿產生器可位在反應 室之外。 __式之簡單說明 爲讓本發明之上述和其他目的、特徵、和優點能更明 顯易懂，下文特舉一較佳實施例，並配合所附圖式，作詳 細說明如下： 第1A圖係繪示一種環矽氧烷類化合物。 第1B圖係繪示一種矽氧烷類化合物。 第2圖係繪示依照本發明一較佳實施例的一種以雙電 漿源來進行化學氣相沈積的示意剖面圖。 圖式之標記說明 200 :晶圓 210 :反應室 220、260 :電源 230 ' 240 :入口 250 :遠距電漿產生器 270、280 :管路 發明之詳細說明 如上所述’在利用化學氣相沈積法來沈積低介電常數 4 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公餐）580523 Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention () It needs to be placed in an appropriate position on the chemical vapor deposition machine, for example, the first electricity award generator can be located in the reaction chamber, and the first The two plasma generators can be located outside the reaction chamber. Simple description of __ formula In order to make the above and other objects, features, and advantages of the present invention more comprehensible, a preferred embodiment is given below in conjunction with the accompanying drawings for detailed description as follows: FIG. 1A The system shows a cyclosiloxane compound. Figure 1B shows a siloxane compound. Fig. 2 is a schematic cross-sectional view of a chemical vapor deposition using a dual plasma source according to a preferred embodiment of the present invention. Explanation of the marks in the drawings: 200: wafer 210: reaction chamber 220, 260: power supply 230 '240: inlet 250: remote plasma generator 270, 280: detailed description of the piping invention as described above' Deposition method to deposit low dielectric constant 4 This paper size is applicable to China National Standard (CNS) A4 specifications (210 X 297 meals)
------------------ -訂- - - ----I (請先閱讀背面之注意事項再本頁) I 經濟部智慧財產局員工消費合作社印製 580523 A7 _____ B7 五、發明說明（） 材料時’其所需之反應氣體不只一種，而且從不同反應氣 體要得到不同反應中間物之所需活化能也大小不一。例如 低介電常數材料常具有多孔性的結構(porous structure)， 其因爲空氣之介電常數接近1，所以可利用多孔性結耩來 降低介電材料之介電常數，常見之具有多孔性結構的介電 材料例如有含氫的政酸鹽類（hydrogen silsesquioxane ; HSQ)。 若想要利用化學氣相沈積法來沈積此類多孔性介電材 質’則所需之反應中間物最好能具有垣狀(ring)或長鍵狀 (long chain)的結構。例如選擇第1A圖與第1B圖所分別 繪之環矽氧烷類化合物與矽氧烷類化合物作爲化學氣相沈 積法之反應物，如此才容易在所沈積的薄膜中產生孔洞。 第1A圖之環矽氧烷類化合物，其環狀結構是由數個（矽 -氧)單元所串成，每個矽（Si)上有可能接著各種不同的取代 基（R!、R2、R3、R4……），如氫基、烷基、烷氧基等。而 第1B圖之矽氧烷類化合物爲矽上接著四個取代基(R5、R6、 R7、R8)，例如烷基、烷氧基等。若想利用此兩類化合物 與氧氣來形成多孔性介電材質，最好能保留環矽氧烷類化 合物之由數個（Si-Ο)單元所組成之環狀結構，只斷矽與取 代基之間的鍵結。而矽氧烷類化合物，亦是希望能保留 Si-0-Si的結構，而只斷矽與取代基之間的鍵結。 但是因爲環矽氧烷類化合物與矽氧烷類化合物之欲保 留的Si-Ο鍵結的鍵能以及欲使兩者斷裂的Si與取代基之 5------------------ -Order------- I (Please read the notes on the back before this page) System 580523 A7 _____ B7 V. Description of the invention () When materials are used, not only one kind of reaction gas is required, but also the activation energy required to obtain different reaction intermediates from different reaction gases is different. For example, low dielectric constant materials often have a porous structure. Because the dielectric constant of air is close to 1, the porous structure can be used to reduce the dielectric constant of the dielectric material. Commonly, it has a porous structure. Dielectric materials include, for example, hydrogen silsesquioxane (HSQ). If a chemical vapor deposition method is to be used to deposit such a porous dielectric material, the required reaction intermediate should preferably have a ring or long chain structure. For example, the cyclosiloxane compounds and the silicone compounds shown in Figures 1A and 1B are selected as the reactants of the chemical vapor deposition method, so that it is easy to generate holes in the deposited film. The cyclic siloxane compound shown in Figure 1A has a cyclic structure composed of several (silicon-oxygen) units. Each silicon (Si) may be followed by a variety of different substituents (R !, R2, R3, R4 ...), such as hydrogen, alkyl, alkoxy, etc. The siloxane compounds shown in Figure 1B are four substituents on the silicon (R5, R6, R7, R8), such as alkyl and alkoxy. If you want to use these two types of compounds and oxygen to form a porous dielectric material, it is best to retain the cyclic structure of the cyclosiloxane compound composed of several (Si-O) units, and only break the silicon and the substituents. The bond between. Siloxane compounds are also expected to retain the structure of Si-0-Si, and only break the bond between silicon and substituents. However, because of the bond energy of the Si-O bond which is to be retained by the cyclosiloxane compound and the silicone compound,
--------^--------- (請先閱讀背面之注意事項>8^||€本頁) I 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 經濟部智慧財產局員Η消費合作社印製 580523 A7 B7 五、發明說明（） 間鍵結的鍵能大小不一，而且差距頗大（如環矽氧烷類化 合物所適合之產生電漿的應用功率爲200-400 W，而矽氧 烷類化合物所適合之產生電漿的應用功率爲50-200 W)。 所以若只用一個電漿產生器來產生電漿，要不是只能在很 小的製程寬度(process window)下進行，不然就是根本無法 找出適宜的條件來符合這兩種不同反應物之所需。因此要 如何控制電漿產生器的功率才能符合不同氣體之個別所需 之活化能，此成爲一個亟待解決的問題。 在習知之化學氣相沈積機台中，除了反應室中的電漿 產生器之外，還會配備有一遠距電漿產生器。遠距電漿產 生器主要是用來產生遠距電漿(remote Plasma) ’然後利用 此遠距電漿來溫和地淸理反應室之室壁上附著的污染物， 以增加化學氣相沈積機台的使用壽命。因此可在不需變更 化學氣相沈積機台的設計下，利用此遠距電漿產生器以不 同的功率來活化其中一種反應氣體，如此可大大增加此化 學氣相沈積製程之裕度。 請參照第2圖，其繪示依照本發明一較佳實施例的一 種以雙電漿源來進行化學氣相沈積的示意剖面圖。在第2 圖中，晶圓200置於化學氣相沈積機台之反應室210中。 反應室210配備有電源220，所以可在反應室210中產生 電漿。在距離反應室210 —段距離之處，配置有遠距電漿 產生器250，其上亦配備有電源260，所以亦可在遠距電 漿產生器250中產生電漿。遠距電漿產生器250所產生之 6 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） ------看--------π---------筹.. (請先閱讀背面之注意事項耳lyk— ^ 580523 A7-------- ^ --------- (Please read the precautions on the back first> 8 ^ || € This page) I This paper size is applicable to China National Standard (CNS) A4 specifications ( 210 X 297 mm) Printed by a member of the Intellectual Property Bureau of the Ministry of Economic Affairs and Consumer Cooperatives 580523 A7 B7 V. Description of the invention () The bond energies of the bonds are different in size, and the gap is quite large (such as suitable for cyclosiloxane compounds) (The application power for generating plasma is 200-400 W, and the suitable power for generating plasma for siloxane compounds is 50-200 W). So if only one plasma generator is used to generate the plasma, either it can only be performed in a small process window, otherwise it is impossible to find suitable conditions to meet the requirements of these two different reactants. need. Therefore, how to control the power of the plasma generator in order to meet the individual activation energy of different gases has become an urgent problem. In the conventional chemical vapor deposition machine, in addition to the plasma generator in the reaction chamber, a remote plasma generator is also provided. The remote plasma generator is mainly used to generate remote plasma (remote Plasma) 'and then use this remote plasma to gently clean the pollutants attached to the wall of the reaction chamber to increase the chemical vapor deposition machine The life of the table. Therefore, without changing the design of the chemical vapor deposition machine, the remote plasma generator can be used to activate one of the reactive gases with different power, which can greatly increase the margin of the chemical vapor deposition process. Please refer to FIG. 2, which illustrates a schematic cross-sectional view of a dual plasma source for chemical vapor deposition in accordance with a preferred embodiment of the present invention. In FIG. 2, the wafer 200 is placed in a reaction chamber 210 of a chemical vapor deposition machine. The reaction chamber 210 is equipped with a power source 220, so that a plasma can be generated in the reaction chamber 210. At a distance from the reaction chamber 210, a remote plasma generator 250 is provided, and a power source 260 is also provided thereon, so the plasma can also be generated in the remote plasma generator 250. The 6 paper sizes produced by the long-range plasma generator 250 are applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) ------ see -------- π ---- ----- Raise .. (Please read the notes on the back first lyk— ^ 580523 A7
五、發明說明（） 經濟部智慧財產局員工消費合作社印製 電漿可經由管路270輸送至反應室210中。 因此若在進行化學氣相沈積時所用的數種反應氣體需 要差距頗大的不同活化能時，可以讓一群活化能相近的數 種反應氣體由入口 230導入，然後經由管路280通人反應 室210中，控制電源22〇供給合適的功率，使這數種反應 氣體在反應室21〇中形成電漿。而另一群活化能相近的數 種反應氣體可由入口 240導入’控制電源260供給合適的 功率，使這數種反應氣體在遠距電獎產生器250處產生電 漿，再經由管路270將電漿通入反應室210中。如此’在 反應室210中就可以混合兩群由不同功率所產生的電漿以 進行化學反應，在晶圓表面沈積出所需之薄膜。 上述使用電源220在反應室210產生電漿的方式以及 使用電源260在遠距電漿產生器250產生電漿的方式包括 射頻（radio frequency ; RF)、微波（microwave)、電子迴旋 共振（electron cyclotron resonance ; ECR)、誘發稱合電漿 (inductive coupled plasma ; ICP)等等各種方式。而化學氣 相沈積機台也不限於只用兩個電漿產生器，若遇到需要提 供兩種以上的不同功率來活化數種不同的反應氣體時，亦 可使化學氣相沈積機台配備兩個以上的電漿產生器以符合 所需。 由上述本發明較佳實施例可知，應用本發明可以讓具 有不同活化能且活化能差距較大的數種反應氣體同時分別 得到其所需之適合的活化能，然後分別產生所需的反應中 7 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） ——!t--------^--------- (請先閱讀背面之注意事項本頁)_ 580523 A7 B7 五、發明說明（） 間物，以利所沈積出之薄膜具有所需的微觀結構來達成薄 膜材料所需之物理化學性質。 雖然本發明已以一較佳實施例揭露如上，然其並非用 以限疋本發明。任何熟習此技藝者，在不脫離本發明之精 神和範@內，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爲準。 (請先閱讀背面之注意事項本頁) tr---------希· 經濟部智慧財產局員工消費合作社印製 衣紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公餐) "----V. Description of the invention () Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs Plasma can be transported to the reaction chamber 210 via the pipeline 270. Therefore, if several reaction gases used in chemical vapor deposition require different activation energies with large gaps, a group of several reaction gases with similar activation energies can be introduced through the inlet 230 and then passed to the reaction chamber through the pipeline 280. In 210, the control power source 22o supplies appropriate power so that the several reaction gases form a plasma in the reaction chamber 21o. Another group of several reaction gases with similar activation energy can be introduced from the inlet 240 to control the power supply 260 to supply appropriate power, so that these several reaction gases generate plasma at the remote electricity award generator 250, and then the electricity is supplied through the pipeline 270. The slurry is passed into the reaction chamber 210. In this way, in the reaction chamber 210, two groups of plasmas generated by different powers can be mixed to perform a chemical reaction, and a desired film can be deposited on the wafer surface. The above-mentioned manner of using the power source 220 to generate the plasma in the reaction chamber 210 and the method of using the power source 260 to generate the plasma at the remote plasma generator 250 include radio frequency (RF), microwave (microwave), and electron cyclotron resonance (electron cyclotron). resonance; ECR), inductive coupled plasma (ICP) and so on. The chemical vapor deposition machine is not limited to using only two plasma generators. If it is required to provide more than two different powers to activate several different reaction gases, the chemical vapor deposition machine can also be equipped with More than two plasma generators to meet your needs. It can be known from the foregoing preferred embodiments of the present invention that the application of the present invention can allow several reactive gases with different activation energies and large differences in activation energies to obtain the appropriate activation energies respectively required at the same time, and then generate the required reactions separately. 7 This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) ——! T -------- ^ --------- (Please read the notes on the back first (This page) _ 580523 A7 B7 V. Description of the invention () Interlayer, so that the deposited film has the required microstructure to achieve the required physical and chemical properties of the film material. Although the present invention has been disclosed above with a preferred embodiment, it is not intended to limit the present invention. Anyone skilled in this art can make various modifications and retouching without departing from the spirit and scope of the present invention. Therefore, the protection scope of the present invention shall be determined by the scope of the attached patent application. (Please read the caution page on the back first) tr --------- Greek · Intellectual Property Bureau of the Ministry of Economic Affairs, consumer clothing cooperatives, printed paper standards for China National Standard (CNS) A4 (210 X 297 public) Meal) " ----