201145387 六、發明說明： 【發明所屬之技術領域】 本發明係關於一種將原料氣體形成為電漿狀態而於基板 上進行成膜的電漿成膜裝置及方法。 【先前技術】 電漿成膜裝置，例如電漿CVD(ChemiCal Vapor Dep〇sm〇n， 化學氣相沈積）裝置係將原料氣體形成為電毁狀態，使電 聚狀態之原料氣體彼此反應而於基板上進行成膜。成膜 時，因提高所形成之膜之膜質之目的等理由而多會對基板 施加偏壓（bias)。 [先前技術文獻] [專利文獻] [專利文獻1]曰本專利特開平5-82629號公報 【發明内容】 [發明所欲解決之問題] 對基板施加偏壓而進行成膜時，存在基板外周部分之膜 厚增高，無法獲得所期望之膜厚均勻性的情形。尤其是絕 緣系膜、例如氮化矽膜、硼氮炔（b〇razine)膜等具有基板 外周部分之膜厚增尚之傾向。例如’改變偏壓(LF)之施加 電壓’對利用先前之電聚CVD裝置形成的硼氮炔膜測定半 徑方向（X軸位置）之膜厚，且將所測定之結果示於圖5。由 圖5可知，當LF為〇 W，即偏壓施加為〇時，基板外周部分 (參照圖5中之區域A)之膜厚稍低於基板中心部分相對於 此’當LF為50 W、100 W、180霣時，即施加有偏壓時， 153993.doc 201145387 基板外周部分（參照圖5中之區域A)之膜厚高於基板中心部 分’無法獲得所期望之膜厚均勻性。 本發明係鑒於上述課題研究而成者，本發明之目的在於 提供一種可提高膜厚均勻性之電漿成膜裝置及方法。 [解決問題之技術手段] 解決上述課題之第1發明之電漿成膜裝置係在將原料氣 體形成為電毁狀態，使電漿狀態之上述原料氣體彼此反應 而於基板上進行成膜時’對上述基板施加偏壓者，其特徵 在於： 將對上述基板施加偏壓之電極之尺寸設為大於上述某 板。 解決上述課題之第2發明之電漿成膜装置係如上述第1發 明之電漿成膜裝置，其中 將上述基板之半徑設為R1，將上述電極之尺寸設為尺2 時， (R2-R1)至少為1 mm以上。 解決上述課題之第3發明之電漿成膜方法係在將原料氣 體形成為電漿狀態’使電漿狀態之上述原料氣體彼此反應 而於基板上進行成膜時，對上述基板施加偏壓者，其特徵 在於： 使用大於上述基板之尺寸之電極對上述基板施加偏壓。 [發明之效果] 根據本發明，由於係將對基板施加偏壓之電極之尺寸設 為大於基板之尺寸，故而可抑制基板外周部分之膜厚增 153993.doc 201145387 加’可提高膜厚均勻性。 【實施方式】 以下’使用圖1〜圖4 ’就本發明之電漿處理裝置及方法 之實施形態進行說明。 (實施例1) 、圖1係表示本發明之電漿處理裝置之實施形態之一例的 透視側視圖’圖2係表示圖！所示之電衆處理裝置中之偏壓 施加用電極的概略構成圖。 首先，使用圖1說明本實施例之電漿處理裝置。再者’ 圖1中係不出ICP(Inductively c〇upled ρι&_，感應麵合電 幻型之電衆CVD裝置1作為一例，但只要具有電聚產生機 構則可為任意裝置。 本實施例之電聚CVD裝置1中，目筒狀之真空室2之内部 構成為成膜室，於真空室2之上部開口部.，以阻擋開口部 之方式配設有陶瓷製的圓板狀之蓋板3。 又於蓋板3之上部（正上方），例如酉己置有包含複數個 圓環之高頻天線4，高頻天線4上經由匹配器5而連接有高 頻電源6。該高頻電源6可對高頻天線4供給較後述低頻電 源13高之振£頻率（例如’ 13 56 MHz)，可透過蓋板3將在 真工至2内生成電漿之電磁波射入。此即為所謂❹型之電 漿產生機構之構成。利㈣p型之t聚產生機構可形成電 子密度較高之電漿。 又’於真空室2之下部具備支持台7、及安裝於支持台7 上之靜電吸盤8’於該靜電吸盤8之上表面，靜電吸附保持 153993.doc 201145387 有包含Si(矽）等半導體材料的圓板狀之基板w。靜電吸盤8 例如係使用氮化鋁（A1N)等陶瓷材料而形成為圓板狀。 又’支持台7之位置可藉由升降裝置9而上下升降，從而在 成膜時可調整真空室2内產生之電漿與基板w之距離。 又，於靜電吸盤8上設置有圓板狀之電極丨丨，於電極^ 上經由匹配器12而連接有低頻電源13。低頻電源13對電極 11施加相比尚頻電源6較低之振盈頻率（例如，4 MHz)，從 而可對基板W施加偏壓。再者，本實施例之電極丨丨係形成 為圓板狀，但是例如當基板w具有定向平面（〇rientati〇nBACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a plasma film forming apparatus and method for forming a film on a substrate by forming a material gas into a plasma state. [Prior Art] A plasma film forming apparatus, such as a plasma CVD (ChemiCal Vapor Dep〇sm〇n, chemical vapor deposition) apparatus, forms a raw material gas into an electric-disrupted state, and reacts the raw material gases in an electropolymerized state with each other. Film formation was performed on the substrate. At the time of film formation, a bias is applied to the substrate for the purpose of improving the film quality of the formed film. [PRIOR ART DOCUMENT] [Patent Document 1] [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei 5-82629. SUMMARY OF THE INVENTION [Problems to be Solved by the Invention] When a film is applied by applying a bias voltage to a substrate, there is a substrate periphery. The film thickness of part is increased, and the desired film thickness uniformity cannot be obtained. In particular, an insulating film such as a tantalum nitride film or a bronazine film has a tendency to increase the film thickness of the outer peripheral portion of the substrate. For example, 'the applied voltage of the bias voltage (LF)' is measured for the film thickness in the radial direction (X-axis position) of the boron nitride film formed by the conventional electropolymerization CVD apparatus, and the results of the measurement are shown in Fig. 5. As can be seen from FIG. 5, when LF is 〇W, that is, the bias is applied as 〇, the film thickness of the outer peripheral portion of the substrate (refer to the region A in FIG. 5) is slightly lower than the central portion of the substrate relative to this 'when the LF is 50 W, When 100 W and 180 施加, that is, when a bias voltage is applied, the film thickness of the outer peripheral portion of the substrate (refer to the region A in FIG. 5) is higher than the central portion of the substrate, and the desired film thickness uniformity cannot be obtained. The present invention has been made in view of the above problems, and an object of the present invention is to provide a plasma film forming apparatus and method which can improve film thickness uniformity. [Means for Solving the Problem] The plasma film forming apparatus according to the first aspect of the present invention is configured such that when the material gas is formed in an electrically destroyed state and the material gases in the plasma state are reacted with each other to form a film on the substrate. When a bias is applied to the substrate, the size of the electrode to which the substrate is biased is set to be larger than the above-described one. The plasma film forming apparatus according to the first aspect of the invention, wherein the radius of the substrate is R1 and the size of the electrode is 2, (R2- R1) is at least 1 mm or more. In the plasma film forming method according to the third aspect of the present invention, when the material gas is formed into a plasma state and the material gases in the plasma state are reacted with each other to form a film on the substrate, a bias is applied to the substrate. The method is characterized in that a bias voltage is applied to the substrate by using an electrode larger than the size of the substrate. [Effects of the Invention] According to the present invention, since the size of the electrode for biasing the substrate is made larger than the size of the substrate, the film thickness of the outer peripheral portion of the substrate can be suppressed from increasing 153993.doc 201145387 plus "can increase film thickness uniformity" . [Embodiment] Hereinafter, embodiments of a plasma processing apparatus and method of the present invention will be described with reference to Figs. 1 to 4'. (Embodiment 1) FIG. 1 is a perspective side view showing an embodiment of a plasma processing apparatus according to the present invention. FIG. 2 is a view showing a diagram! A schematic configuration diagram of the bias application electrode in the battery processing device shown. First, the plasma processing apparatus of this embodiment will be described using FIG. In addition, in FIG. 1, the ICP (Inductively C 〇 led ρ , 感应 感应 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 In the electro-polymerization CVD apparatus 1, the inside of the cylindrical vacuum chamber 2 is configured as a film forming chamber, and is opened at the upper portion of the vacuum chamber 2. The ceramic disc-shaped cover is disposed to block the opening. The plate 3. Also on the upper portion (directly above) of the cover plate 3, for example, a high frequency antenna 4 including a plurality of rings is placed, and the high frequency power supply 6 is connected to the high frequency antenna 4 via the matching device 5. The frequency power source 6 can supply the high frequency antenna 4 with a higher frequency (for example, '13 56 MHz) than the low frequency power source 13 to be described later, and can inject electromagnetic waves generated by the plasma in the real work up to 2 through the cover plate 3. It is a so-called 电-type plasma generating mechanism. The (iv) p-type t-generating mechanism can form a plasma with a high electron density. Also, a support table 7 is provided below the vacuum chamber 2, and is mounted on the support table 7. The electrostatic chuck 8' is on the upper surface of the electrostatic chuck 8, and the electrostatic adsorption is maintained 153993.doc 20114 5387 has a disk-shaped substrate w containing a semiconductor material such as Si. The electrostatic chuck 8 is formed into a disk shape by using a ceramic material such as aluminum nitride (A1N), for example, and the position of the support table 7 can be The lifting device 9 is lifted up and down to adjust the distance between the plasma generated in the vacuum chamber 2 and the substrate w at the time of film formation. Further, the electrostatic chuck 8 is provided with a disk-shaped electrode 丨丨, and is connected to the electrode The matching device 12 is connected to the low frequency power supply 13. The low frequency power supply 13 applies a lower vibration frequency (for example, 4 MHz) to the electrode 11 than the frequency power supply 6, so that the substrate W can be biased. The electrode lanthanide is formed into a disk shape, but for example, when the substrate w has an orientation plane (〇rientati〇n
Flat)時，電極11只要形成為與基板之形狀相似之形狀即 可0 又，於支持台7上設置有控制基板w之溫度之加熱器、 冷媒流路等溫度控制裝置，藉由溫度控制裝置（省略圖示） 可將基板W a又疋為所期望之溫度（例如，1 5 〇〜7 〇 〇。〇)。 另外，基板W係將設置於真空室2之側壁之閘門 d〇〇r)17打開而搬送至靜電吸盤8上，且將基板…載置於靜 電吸盤8上之後，關閉閘門17，於真空室2内部實施後述之 製程。 又，於真空室2之侧壁部分的較蓋板3低且較支持台了高 之位置，設置有複數個喷氣嘴14，可藉由氣體控制裝置15 之控制，而自喷氣嘴14向真空室2内部供給所期望之流量 之氣體。 又，真空室2中設置有壓力控制裝置（真空泵、壓力控制 閥、真空計等；省略圖示）’使用真空泵自底部側排出真 153993.doc 201145387 空室2内部之氣體，並且使用真空計、壓力控制閥將真空 室2内部調整為所期望之壓力。 另外’上述高頻電源6、升降裝置9、低頻電源13、氣體 控制裝置15、溫度控制裝置及壓力控制裝置等由主控制裝 置16綜合控制，該主控制裝置16係根據預先設定的所期望 之製程步驟、製程條件而進行控制。 以下’參照圖2說明本實施例之電漿CVD裝置1中的電極 11之構成。另外，於圖6中示出先前之偏壓施加用電極之 構成以作比較。 如圖ό所示’先前之電漿CVD裝置中，設置於靜電吸盤 2 1上之偏壓施加用電極22之尺寸係設為稍小於基板| ^例 如’將基板W之半徑設為R1，電極22之半徑設為R2，係藉 由使R2=Rl-i.〇mm*形成為R1>R2之關係。 相對於此，本實施例之電漿CVD裝置1如圖2所示，係將 偏壓施加用電極丨丨之尺寸設為大於基板W ^例如，將基板 w之半控設為R1，電極丨丨之半徑設為R2，係形成&R1<R2 之關係。 使用圖3、圖4對使用上述構成之電極丨丨的成膜結果進行 說明。該圖3係改變之條件而測定基板外周部 之膜厚變化所繪製者，圖4係根據圖3之結果，將基板外周 部分之膜厚上升率與AR之關係繪製成曲線的圖。再者， 圖3、圖4中亦同時記載有使用先前之電極22的成膜結果以 作比較。又’作為製程之條件，係將基板w之直徑設為 3〇〇 mm(半徑Ri = 150 mm)，kLF=18〇 w下形成硼氮炔膜作 153993.doc 201145387 為薄膜。該條件係使用先前之電極22時基板外周部之膜厚 會增厚之製程條件。 於圖3所示之曲線圖中，ARs-l mm係表示使用先前之電 極22的成膜結果。根據圖3可知，AR=-1 mm之情形時，隨 著靠近基板W之外緣，所形成之硼氮炔膜之膜厚顯著增 厚。推測其主要原因在於，對基板w施加偏壓時，基板w 之外周部分之電場強度增強，其結果基板外周部分之成膜 速率提尚。 另一方面’滿足本實施例之條件的AR=+4 mm之情形 時，儘管隨著靠近基板w之外緣，所形成之硼线膜之膜 厚增厚’但其增厚傾向顯著改善，㈣足本實施例之條件 的ΔΚ-+9、+14、+19 mm之情形時，其傾向進一步改善。 推測其主要原因在於，由於電極u之尺寸大於基板w之尺 寸，因此對基板W施加偏壓時，位於較基板W之外緣更外 側的電極11之外周部分的電場強度增強其結果基板外周 部分之成膜速率相較先前得到抑制。 根據圖3之v、。果，將距離基板中心丄之位置（距離基 板邊緣10 mm之位置）之膜厚設為丁丨，距離基板中心147 mm之位f (距離基板邊緣3 _之位置）之膜厚設為丁2，將 各條件下之外周膜厚上升率=(T2_T1)/Tuf於曲線上，得到 圖4通常’所形成之薄膜之均勻性較理想的是基板面内 之最大值〜最小值在6%以内，考慮到此事項，則至少使 △RU随即可獲得所期望之均句性。又，欲使基板面内 之最大值〜最小值在3%以内之情形時，則至少使△似随 153993.doc 201145387 即可。另外’當ΔΙ12 9 mm時’外周膜厚上升率達到最 低，故而此時最可提高均勻性。 再者’此處係示出基板W之直徑為300 mm之情形，於基 - 板W之直徑小於3〇〇 mm(例如’直徑為200 mm、150 mm 等）之情形時’靜電吸盤會更換成符合基板直徑之尺寸的 靜電吸盤，因此變成R1>R2之關係，仍然可見基板外周部 之膜厚增高之傾向。因此，若於基板W之直徑小於3〇〇 之情形時亦形成為R1<R2之關係，則可改善面内均勻性。 如上所述’藉由構成為偏壓施加用電極之尺寸大於基 板，可提高形成於基板上之薄膜的膜厚均勻性。又，抑制 基板外周部分之膜厚增加可緩和該部分之膜應力，其結果 亦可防止薄膜剝離，抑制微粒之產生。 以下，參照圖1所示之電漿CVD裝置丨對硼氮炔膜之成膜 製程進行說明。再者，本發明並不僅限於硼氮炔膜，亦可 應用於氮化矽膜等其他絕緣系膜。 首先’就形成蝴氮快膜時所使用之原料氣體進行說明。 $ A ^ H A g 所供給之原料氣體係使用以下之化學式 一、，元土侧氮炔化合物（alkylborazine compound)及載 氣。 [化1]In the case of the flat electrode, the electrode 11 may be formed in a shape similar to the shape of the substrate. The support table 7 is provided with a temperature control device such as a heater for controlling the temperature of the substrate w and a refrigerant flow path, and the temperature control device is provided. (The illustration is omitted) The substrate Wa can be turned into a desired temperature (for example, 1 5 〇 to 7 〇〇. 〇). Further, the substrate W is opened by the shutter d〇〇r) 17 provided on the side wall of the vacuum chamber 2, and is transported to the electrostatic chuck 8, and after the substrate is placed on the electrostatic chuck 8, the shutter 17 is closed, in the vacuum chamber. 2 Internally implement the process described later. Moreover, in the side wall portion of the vacuum chamber 2 which is lower than the cover plate 3 and higher than the support table, a plurality of air nozzles 14 are provided, which can be controlled by the gas control device 15 from the air nozzle 14 to the vacuum. The chamber 2 supplies a gas of a desired flow rate. Further, the vacuum chamber 2 is provided with a pressure control device (a vacuum pump, a pressure control valve, a vacuum gauge, etc.; abbreviate|omitted). The vacuum gas pump is used to discharge the gas inside the empty chamber 2 from the bottom side, and a vacuum gauge is used. The pressure control valve adjusts the inside of the vacuum chamber 2 to a desired pressure. Further, the above-described high-frequency power source 6, lifting device 9, low-frequency power source 13, gas control device 15, temperature control device, pressure control device, and the like are integrally controlled by the main control device 16, which is based on a predetermined setting. Process steps and process conditions are controlled. The configuration of the electrode 11 in the plasma CVD apparatus 1 of the present embodiment will be described below with reference to Fig. 2 . Further, the configuration of the previous bias applying electrode is shown in Fig. 6 for comparison. As shown in FIG. ', in the prior plasma CVD apparatus, the size of the bias application electrode 22 provided on the electrostatic chuck 21 is set to be slightly smaller than the substrate|^, for example, the radius of the substrate W is set to R1, and the electrode The radius of 22 is set to R2 by forming R2 = Rl - i. 〇 mm * into the relationship of R1 > R2. On the other hand, in the plasma CVD apparatus 1 of the present embodiment, as shown in FIG. 2, the size of the bias applying electrode 丨丨 is set to be larger than the substrate W^, for example, the half of the substrate w is set to R1, and the electrode 丨The radius of 丨 is set to R2, which forms the relationship between &R1<R2. The film formation result using the electrode crucible of the above configuration will be described with reference to Figs. 3 and 4 . Fig. 3 is a graph showing changes in the film thickness of the outer peripheral portion of the substrate, and Fig. 4 is a graph in which the relationship between the film thickness increase rate of the outer peripheral portion of the substrate and AR is plotted as a result of Fig. 3 . Further, the film formation results of the previous electrode 22 are also described in Fig. 3 and Fig. 4 for comparison. Further, as a condition of the process, the diameter of the substrate w was set to 3 〇〇 mm (radius Ri = 150 mm), and the borozepine film was formed at KK 993 = 18 〇 w as 153993.doc 201145387 as a film. This condition is a process condition in which the film thickness of the outer peripheral portion of the substrate is increased when the previous electrode 22 is used. In the graph shown in Fig. 3, ARs-1 mm indicates the film formation result using the previous electrode 22. As is apparent from Fig. 3, in the case of AR = -1 mm, the film thickness of the formed boron azynyne film is remarkably thickened as it approaches the outer edge of the substrate W. It is presumed that the main reason is that when a bias voltage is applied to the substrate w, the electric field intensity of the outer peripheral portion of the substrate w is enhanced, and as a result, the film formation rate of the outer peripheral portion of the substrate is improved. On the other hand, in the case where AR = +4 mm satisfying the conditions of the present embodiment, although the film thickness of the formed boron wire film is thickened as it approaches the outer edge of the substrate w, the tendency to thicken is remarkably improved. (4) In the case of the conditions of ΔΚ-+9, +14, and +19 mm of the present embodiment, the tendency is further improved. It is presumed that the main reason is that since the size of the electrode u is larger than the size of the substrate w, when a bias voltage is applied to the substrate W, the electric field intensity of the outer peripheral portion of the electrode 11 located outside the outer edge of the substrate W is enhanced. The film formation rate is suppressed compared to the previous one. According to v of Figure 3. The film thickness from the center of the substrate (10 mm from the edge of the substrate) is set to 丨, and the film thickness of 147 mm from the center of the substrate (position from the edge of the substrate 3 _) is set to 2 Under the conditions, the outer film thickness rise rate = (T2_T1) / Tuf on the curve under all conditions, the uniformity of the film formed in the general view of Fig. 4 is preferably the maximum value within the substrate surface to the minimum value within 6%. In view of this matter, at least the ΔRU can be obtained with the desired uniformity. Further, in the case where the maximum value to the minimum value in the plane of the substrate are within 3%, at least Δ is required to follow 153993.doc 201145387. Further, when ΔΙ 12 9 mm, the outer peripheral film thickness increase rate is the lowest, so that the uniformity can be improved most at this time. Furthermore, 'the case where the diameter of the substrate W is 300 mm is shown here, and the electrostatic chuck is replaced when the diameter of the base-plate W is less than 3 mm (for example, 'diameter is 200 mm, 150 mm, etc.) Since the electrostatic chuck conforms to the size of the substrate diameter, the relationship between R1 and R2 is maintained, and the film thickness of the outer peripheral portion of the substrate tends to increase. Therefore, if the diameter of the substrate W is less than 3 亦, the relationship of R1 < R2 is also formed, whereby the in-plane uniformity can be improved. As described above, the film thickness uniformity of the film formed on the substrate can be improved by making the electrode for bias application larger than the substrate. Further, suppressing an increase in the film thickness of the outer peripheral portion of the substrate can alleviate the film stress in the portion, and as a result, peeling of the film can be prevented, and generation of fine particles can be suppressed. Hereinafter, the film formation process of the borozepine film will be described with reference to the plasma CVD apparatus shown in Fig. 1. Further, the present invention is not limited to the boron azepine film, and can be applied to other insulating film such as a tantalum nitride film. First, the raw material gas used in the formation of the nitrogen fast film will be described. The raw material gas system supplied by $ A ^ H A g uses the following chemical formula I, the alkylborazine compound and the carrier gas. [Chemical 1]
153993.doc 201145387 此處，上述化學式1中之側鏈基Ri〜Re為氫原子或碳數5 以下之烷基，可相同亦可不同。但是排除R1〜l全部為氫 原子之情形。其中’較佳為尺丨、r3、R5之至少"固為氫原 子之烧基蝴氮快化合物。 ' 將上述烷基硼氮炔化合物氣化後，使用惰性氣體作為載 氣而向真空室2中供給。又，載氣通常使用氦氣、氯氣等 稀有氣體或氮氣，亦可使用其等之混合氣體或視需要添加 有氫氣、氧氣、氨氣、曱烷等之混合氣體。再者，烷基硼 氮炔化合物較佳為常溫常壓下為液體之化合物，但只要藉 由加熱等可氣化（昇華）則亦可為固體。 繼而，於電聚CVD裝置上中，使用上述原料氣體實施以 下程序’藉此形成硼氮炔膜。 (步驟1) 使用未圖示之搬送裝置將基板W自閘門17搬送至真空室 2内’載置於靜電吸盤8上並吸附保持。利用溫度控制裝 置，將支持台7及靜電吸盤8控制於烷基硼氮炔化合物不會 液化’且蝴氮炔骨架系分子彼此不會開始縮合之溫度範圍 即1 50 C〜700 C中之任一溫度，藉由溫度控制，可於基板w 之溫度為所期望之設定溫度下實施製程。又，藉由升降裝 置9將基板W之高度位置移動至與蓋板3相距5 cm〜3〇 範圍内之任一位置。 藉由使用升降裝置9拉開自蓋板3至基板W之距離，可與 電浆密度較高之電漿產生區域之間隔開距離而將基板W配 置於來自電漿產生區域之電子擴散而電子減少之電漿擴散 153993.doc 201145387 區域。因此成膜時，可於將藉由電漿而自烷基硼氮炔化合 物中解離之烷基輸送至基板臀表面之前，使該烷基中性分 子化。中性分子化之烷基與硼氮炔骨架系分子再次結合之 機率較低，會直接排出。其結果，當棚氮炔骨架系分子彼 此進行氣相聚合時，烷基導入至硼氮炔膜中之情況減少， 可減少薄膜中之奴量，可提高經氣相聚合之蝴氮炔骨架系 分子之分子量，形成特性優異之膜。 (步驟2) 使用氣體控制裝置1 5，自喷氣嘴14將載氣（例如，He氣 體）供給至真空室2内，利用真空控制裝置將真空室2内之 真工度控制為10〜50 mTorr左右’並且，經由匹配器5自高 頻電源6將頻率13.56 MHz之RF(radio frequency，射頻）功 率供給至高頻天線4，而向真空室2内射入電磁波，使所供 給之氣體電離’從而於真空室2内生成電漿。高頻電源6供 給之RF功率係至一連串製程結束為止控制為電漿穩定地點 火’且可不破壞硼氮炔骨架結構地將硼氮炔骨架系分子之 側鏈基解離的電力範圍即8〇〇 W/m2〜53000 W/m2之任一電 力。再者’自噴氣嘴14供給之载氣之流量係至一連串製程 …束為止控制為適宜之流量’較佳為2〇〇 sccni〜i 〇〇〇 seem 左右® (步驟3) 電毁穩定後’自低頻電源13經由匹配器12將頻率4 MHz 之LF功率供給至電極丨丨，並且自喷氣嘴丨4將經氣化的化學 式1所不之烷基硼氮炔化合物以逐漸增加之方式供給至真 153993.doc 201145387 空室2内直至達到特定量為止，將真空室2内之真空度控制 為10~50 mTorr左右。此時，低頻電源13供給之LF功率（偏 壓功率）係於成膜製程中控制為14500 W/m2以下之電力。 施加LF功率時，硼氮炔骨架系分子彼此之氣相聚合受到促 進’因此具有不僅膜之機械強度提高，且耐水性、耐熱 性、耐化學品性亦得到改善之優點。 再者’亦可與烷基硼氮炔化合物一起供給選自由氨氣及 包含碳數1〜3之烷基之胺化合物（例如，C2H5NH2)所組成之 群中的至少1種，例如供給2〇〇 sccm左右。自院基侧氮炔 化合物解離之烷基較理想的是不導入至所形成之硼氮炔膜 中，藉由使用選自由氨氣及包含碳數之烷基之胺化合 物所組成之群中的至少〗種，可更高效率地將烷基中性分 子化，使得該烷基不會導入至所形成之硼氮炔膜中。例 如，作為碳數為2之胺化合物有乙胺（C：2H5NH2)，若使解離 之烷基與將乙胺解離所得者進行反應，則形成作為中性分 子之烷基胺，該烷基胺與硼氮炔骨架系分子再次結合之機 率較低，因此會直接排出。 又，供給氨氣、包含碳數之烷基之胺化合物等除減 /%、元基導入至侧氮炔膜中之情況以外，亦具有下述效果： 形成為自氨氣、包含碳數卜3之院基之胺化合物等解離之 氮作為間隔物（spaeer)而進人至硼氮炔骨架結構彼此之交 聯之間的、（構（Β_Ν·Β結合），從而硼氮炔骨架結構彼此難 以縮合。 藉由以上之製程條件’成膜步财之成膜反應進行。具 I53993.doc 12 201145387 體而言’烷基硼氮炔化合物中之硼氮炔骨架系分子（硼氮 快環）與側鏈基藉由電漿而解離，形成為電漿狀態之硼氮 快骨架系分子彼此進行氣相聚合並吸附於基板w上，藉此 形成所期望之硼氮炔膜。 (步驟4) 實施特定時間之成膜步驟，於基板W上形成所期望之膜 厚之棚氮快膜後，結束成膜步驟，繼而實施反應促進步 驟。具體而言，將對電極丨丨供給之來自於低頻電源13的1^ 功率设為大於成膜步驟中之LF功率，並且逐漸減少自喷氣 嘴14供給至真空室2内之烷基硼氮炔化合物氨氣、包含 碳數1〜3之烷基之胺化合物等，使真空室2内僅存在不與硼 氮炔膜本身反應之稀有氣體（He、Ar等）或乂等惰性氣體， 並將真空室2内之真空度控制為1〇〜5〇 mT〇rr左右。於該反 應促進步驟中，低頻電源丨3之[LF功率X施加時間]為 0 W/m s以上，且其功率係控制為1;274〇〇 w/m2以 了之電力。該條件係使硼氮炔骨架系分子彼此之交聯反應 又J促進但不會對薄膜造成損傷之條件。如此，藉由以 上之製程條件，反應促進步驟之反應促進實現’即蝴氮诀 骨架系分子彼此之交聯反應得到促進。 於該反應促進步驟中’藉由使成膜步驟所形成之硼氮块 膜中殘存的反應活性基縮合而促進交聯反應，並且除去& H結合。因此，藉由促 , 聯反應’可促進膜進-步降低 Β Ηέ:、’且’藉由除去成為與水分反應之活性部位的 .·、、，。合可抑制經時變化’從而提高穩定性。又，藉由促 I53993.doc 201145387 進交聯反應，可實現更高之機械強度（機械強度楊式模數 為10 GPa以上），其結果將使耐化學品性提高、加工性提 高、CMP(Chemical Meehanieal pGlish，化學機械研磨）耐 受性提高。另夕卜’由於係使用與有機系高分子材料相比对 熱性優異之無機高分子系材料，故而亦可達成财熱化。 藉由實施上述程序’可實現具備低介電係數、低漏電 流、高機械強度之特性的硼氮炔膜，$而可實現該等特性 之經時變化較小之侧氮炔膜。例如，作為其具體特性，可 降低介電係數（比介電係、數為3 5以下）、降低漏電流（漏電 流為5E-8 A/cm2以下）、提高機械強度（楊式模數為i〇 Gpa 以上），並且作為特性之穩定性，可實現比介電係數之穩 定性（比介電係數之經時變化為〇〗以下）。 [產業上之可利用性] 本發明適合於施加偏壓而成膜之薄膜，例如硼氮快膜或 氮化矽膜等。 ' 【圖式簡單說明】 圖1係表示本發明之電漿處理裝置之實施形態之一例的 透視側視圖； 圖2係表示圖！所示之電漿處理裝置中之偏壓施加用電極 的概略構成圖； 圖3係改變从：⑽』i)之條件而敎基板外周部之膜厚 變化所繪製的曲線圖； 圖4係根據圖3之結果，將基板外周部分之膜厚上升率與 △R之關係繪製成曲線的圖； 153993.doc 201145387 圖5係表示改變偏壓（LF)之施加電壓而對利用先前之電 漿CVD裝置所形成之硼氮炔膜的半徑方向（X軸位置）之膜 厚進行測定之結果的曲線圖；及 圖6係表示先前之偏壓施加用電極之構成的概略構 圖。 【主要元件符號說明】 1 電漿CVD裝置 2 真空室 3 蓋板 4 高頻天線 5 ^ 12 匹配器 6 高頻電源 7 支持台 8、 21 靜電吸盤 9 升降裝置 11 '22 電極 13 低頻電源 14 噴氣嘴 15 氣體控制裝置 16 主控制裝置 17 閘門 R1 基板之半徑 R2 電極之半徑 W 基板 153993.doc153993.doc 201145387 Here, the side chain groups Ri to Re in the above Chemical Formula 1 may be the same as the hydrogen atom or the alkyl group having 5 or less carbon atoms. However, it is excluded that all of R1 to l are hydrogen atoms. Wherein 'preferably, at least the ruler, r3, and R5" is a hydrogen-based compound of a hydrogen atom. After the above alkylborazine compound is vaporized, it is supplied to the vacuum chamber 2 using an inert gas as a carrier gas. Further, the carrier gas is usually a rare gas such as helium or chlorine, or a nitrogen gas, or a mixed gas such as hydrogen, oxygen, ammonia or decane may be added as needed. Further, the alkylboronium alkyne compound is preferably a compound which is liquid at normal temperature and normal pressure, but may be solid as long as it can be vaporized (sublimation) by heating or the like. Then, in the electropolymerization CVD apparatus, the following procedure was carried out using the above-mentioned source gas to thereby form a boron azine membrane. (Step 1) The substrate W is transferred from the shutter 17 to the inside of the vacuum chamber 2 by a transfer device (not shown), and placed on the electrostatic chuck 8 and sucked and held. By using a temperature control device, the support table 7 and the electrostatic chuck 8 are controlled in a temperature range in which the alkyl boron azepine compound does not liquefy and the cyanide skeleton molecules do not start to condense, that is, 1 50 C to 700 C. At a temperature, by temperature control, the process can be carried out at a desired set temperature at the temperature of the substrate w. Further, the height position of the substrate W is moved by the lifting device 9 to any position within a range of 5 cm to 3 Torr from the cover 3. By using the lifting device 9 to pull apart the distance from the cover plate 3 to the substrate W, the substrate W can be disposed in the electron-derived region from the plasma generating region by the distance between the plasma generating regions having a higher plasma density. Reduce the plasma diffusion 153993.doc 201145387 area. Therefore, when the film is formed, the alkyl group can be neutralized and neutralized before transporting the alkyl group which is dissociated from the alkylborazine compound by plasma to the surface of the substrate buttocks. The neutralized molecular alkyl group and the boron azyne skeleton molecule are less likely to recombine and will be directly discharged. As a result, when the acetyl alkyne skeleton molecules are subjected to gas phase polymerization, the introduction of the alkyl group into the borozepine film is reduced, the amount of the slave in the film can be reduced, and the vapor-polymerized azo alkyne skeleton can be improved. The molecular weight of the molecule forms a film excellent in properties. (Step 2) Using a gas control device 15, a carrier gas (for example, He gas) is supplied from the air nozzle 14 into the vacuum chamber 2, and the vacuum control device controls the true degree in the vacuum chamber 2 to 10 to 50 mTorr. Left and right 'and, RF (radio frequency) power of 13.56 MHz is supplied from the high frequency power source 6 to the high frequency antenna 4 via the matching unit 5, and electromagnetic waves are injected into the vacuum chamber 2 to ionize the supplied gas. Thereby, plasma is generated in the vacuum chamber 2. The RF power supplied from the high-frequency power source 6 is controlled to be a plasma that is stably ignited until the end of a series of processes, and the power range in which the side chain group of the boron azine skeleton molecule is dissociated without breaking the boron azine skeleton structure is 8〇〇. Any power of W/m2~53000 W/m2. Furthermore, the flow rate of the carrier gas supplied from the air nozzle 14 is controlled to a series of processes... the flow rate is controlled as a suitable flow rate. Preferably, it is 2 〇〇 sccni~i 〇〇〇seem or so (step 3) after the electric stagnation is stabilized' The LF power having a frequency of 4 MHz is supplied from the low frequency power source 13 to the electrode 经由 via the matcher 12, and the vaporized sulfonium azide compound of the chemical formula 1 is supplied from the gas nozzle 丨4 to the gradual increase to 153993.doc 201145387 The vacuum in the vacuum chamber 2 is controlled to about 10 to 50 mTorr until the specific amount is reached in the empty chamber 2. At this time, the LF power (bias power) supplied from the low-frequency power source 13 is controlled to be 14500 W/m2 or less in the film forming process. When the LF power is applied, the gas phase polymerization of the boron azine skeleton molecules is promoted. Therefore, not only the mechanical strength of the film is improved, but also the water resistance, heat resistance, and chemical resistance are improved. Further, at least one selected from the group consisting of ammonia gas and an amine compound containing an alkyl group having 1 to 3 carbon atoms (for example, C2H5NH2) may be supplied together with the alkylborazine compound, for example, 2 Å. 〇sccm or so. It is preferred that the alkyl group dissociated from the base alkyne compound is not introduced into the formed boron azynyne film by using a group selected from the group consisting of ammonia gas and an amine compound containing an alkyl group having a carbon number. At least the species can be molecularly molecularly more efficiently such that the alkyl group is not introduced into the formed boron azyne membrane. For example, as the amine compound having a carbon number of 2, there is ethylamine (C: 2H5NH2), and if the alkyl group which is dissociated is reacted with the one obtained by dissociating ethylamine, an alkylamine which is a neutral molecule is formed, and the alkylamine is formed. The possibility of recombination with the boron azapine skeleton molecule is low, so it is directly discharged. Further, in addition to the case where an ammonia gas or an amine compound containing an alkyl group having a carbon number is added, and the elementary group is introduced into the side azynylene film, the following effects are also obtained: the formation is self-ammonia gas, and the carbon number is included. The dissociated nitrogen of the amine compound such as the compound of 3 is introduced as a spacer to the cross-linking between the boron azide skeleton structures (the structure (Β_Ν·Β bond), whereby the boron azyne skeleton structure is mutually It is difficult to condense. It is carried out by the above-mentioned process conditions, film formation reaction of film formation. With I53993.doc 12 201145387, the boron azynylene skeleton molecule in the alkyl boron nitride compound (boron nitrogen fast ring) Dissociating from the side chain groups by plasma, the boron-nitrogen fast skeleton molecules formed in a plasma state are subjected to gas phase polymerization and adsorbed on the substrate w, thereby forming a desired boron azine film. (Step 4) After a film forming step at a specific time, a film-forming film having a desired film thickness is formed on the substrate W, the film forming step is completed, and then a reaction promoting step is performed. Specifically, the counter electrode is supplied from a low-frequency power source. 13's 1^ power is set to be larger than the filming step The LF power in the step, and gradually reduce the ammonia of the alkylborazine compound, the amine compound containing the alkyl group having 1 to 3 carbon atoms, and the like supplied from the air nozzle 14 into the vacuum chamber 2, so that only the vacuum chamber 2 exists. a noble gas (He, Ar, etc.) or an inert gas such as helium which does not react with the boron azide membrane itself, and controls the degree of vacuum in the vacuum chamber 2 to be about 1 〇 5 5 m 〇 rr. The [LF power X application time] of the low-frequency power supply 丨3 is 0 W/ms or more, and its power is controlled to be 1; 274 〇〇 w/m 2 is used for power. This condition is such that the boron-azyne skeleton molecules are mutually The cross-linking reaction promotes, but does not cause damage to the film. Thus, by the above process conditions, the reaction of the reaction-promoting step promotes the realization of the cross-linking reaction between the molecules of the rhodium skeleton. In the reaction promoting step, 'the crosslinking reaction is promoted by condensing the reactive groups remaining in the boron nitride bulk film formed by the film forming step, and the & H bond is removed. Therefore, by promoting, the reaction can be promoted. Membrane advance-down Β 、:, 'and' by dividing It is possible to reduce the change over time to improve the stability of the active sites reactive with moisture. In addition, higher mechanical strength can be achieved by promoting the cross-linking reaction of I53993.doc 201145387 (mechanical The strength of the Young's modulus is 10 GPa or more. As a result, the chemical resistance is improved, the workability is improved, and the resistance to CMP (Chemical Meehanieal pGlish) is improved. In addition, the use of the system is higher than that of the organic system. Since the molecular material is superior to the inorganic polymer material having excellent heat properties, it can also be used for heat generation. By performing the above procedure, a boron azine film having low dielectric constant, low leakage current, and high mechanical strength can be realized. , and a side nitrogen alkyne film having a relatively small change over time can be realized. For example, as a specific characteristic, the dielectric constant (the dielectric system number is 35 or less), the leakage current (the leakage current is 5E-8 A/cm2 or less), and the mechanical strength can be lowered (the Young's modulus is i). 〇Gpa or more), and as the stability of the characteristics, the stability of the specific dielectric coefficient can be achieved (the change with respect to the dielectric constant is 以下 or less). [Industrial Applicability] The present invention is suitable for a film formed by applying a bias voltage, such as a boron-nitrogen fast film or a tantalum nitride film. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a perspective side view showing an embodiment of a plasma processing apparatus according to the present invention; Fig. 2 is a view showing a diagram! FIG. 3 is a graph showing changes in film thickness of the outer peripheral portion of the substrate from the condition of (10) ii); FIG. 3 is a graph based on the change in film thickness of the outer peripheral portion of the substrate; As a result of FIG. 3, the relationship between the film thickness increase rate of the outer peripheral portion of the substrate and ΔR is plotted as a curve; 153993.doc 201145387 FIG. 5 shows the application of the voltage by changing the bias voltage (LF) to the previous plasma CVD. A graph showing the results of measuring the film thickness in the radial direction (X-axis position) of the boron azynyne film formed by the apparatus; and FIG. 6 is a schematic configuration showing the configuration of the prior bias applying electrode. [Main component symbol description] 1 Plasma CVD device 2 Vacuum chamber 3 Cover 4 High frequency antenna 5 ^ 12 Matcher 6 High frequency power supply 7 Support table 8, 21 Electrostatic chuck 9 Lifting device 11 '22 Electrode 13 Low frequency power supply 14 Jet Mouth 15 Gas control device 16 Main control device 17 Gate R1 Radius of the substrate R2 Radius of the electrode W Substrate 153993.doc