201022467 六、發明說明： ‘ 【發明所屬之技術領域】 ' 本發明是有關觸媒化學氣相沉積裝置，其可將原料氣 體供應到裝設在反應室内已加熱的觸媒線上，並使所生成 的分解種沉積在前述反應室内的被成膜基材上而進行成 膜。 【先前技術】 觸媒化學氣相沉積法（CAT-CVD : catalytic-Chemical β Vapor Deposition)是一種成膜方法，例如可將反應氣體 (原料氣體）供應到已加熱到1，500至2, 000°C的觸媒線上 後，利甩反應氣體的觸媒反應或熱分解反應，使生成的分 解種（沉積種）沉積在被成膜基材上。 在使反應氣體的分解種堆積在基材上以進行成膜之 點，觸媒化學氣相沉積法是與電漿CVD法類似。然而，由 於觸媒化學氣相沉積法是利用高溫觸媒線上的反應氣體之 A 觸媒反應或熱分解反應而生成分解種，故在與形成電漿後 ❹ 生成反應氣體的分解種之電漿CVD法比較時，有不因電漿 而損壞表面，且原料氣體的利用效率也較高之優點。 觸媒化學氣相沉積法可使用於例如矽（Si)類膜的成膜 之際。以往，在觸媒化學氣相沉積法中所使用的觸媒線， 是廣用鎢（W)線（例如參照專利文獻1)。然而’鎢與矽之間 容易引起合金化反應（矽化物化）。當鎢成為矽化物時，將 使表面產生龜裂而降低機械強度，以致縮短觸媒線的壽命。 另一方面，組（Ta)是梦化物化速度比鶴還緩慢的材 4 320860 201022467 * 料。也有在觸媒線使用此鈕線而形成矽膜的方法（例如參照 . 專利文獻2) 〇 專利文獻1 : 專利文獻1: 曰本特開2003-303780號公報 曰本特開2003-247062號公報 【發明内容】 (發明所欲解決的問題） 不過’在與鎢比較時，钽的機械強度較低，尤其是高 ❹/JBL中使用時的潛變強度（creep strength)較低。因此，將201022467 VI. Description of the invention: 'Technical field to which the invention pertains' The present invention relates to a catalytic chemical vapor deposition apparatus which supplies a raw material gas to a charged catalyst line installed in a reaction chamber, and generates The decomposed species are deposited on the film-formed substrate in the reaction chamber to form a film. [Prior Art] Catalytic Chemical Vapor Deposition (CAT-CVD) is a film forming method, for example, a reaction gas (raw material gas) can be supplied to have been heated to 1,500 to 2,000. After the catalyst line of °C, the catalytic reaction or thermal decomposition reaction of the reaction gas of Lixon causes the generated decomposition species (deposited species) to be deposited on the film-formed substrate. The catalyst chemical vapor deposition method is similar to the plasma CVD method in that a decomposition product of a reaction gas is deposited on a substrate to form a film. However, since the catalytic chemical vapor deposition method utilizes the A catalyst reaction or the thermal decomposition reaction of the reaction gas on the high temperature catalyst line to generate a decomposition species, the plasma of the decomposition species of the reaction gas is formed after the formation of the plasma. When the CVD method is compared, there is an advantage that the surface is not damaged by the plasma, and the utilization efficiency of the material gas is also high. Catalyst chemical vapor deposition can be used for film formation of, for example, a bismuth (Si) film. Conventionally, a catalyst wire used in a catalytic chemical vapor deposition method is a tungsten (W) wire (see, for example, Patent Document 1). However, the alloying reaction (deuteration) is easily caused between tungsten and tantalum. When tungsten becomes a telluride, cracks are formed on the surface to lower the mechanical strength, so that the life of the catalyst wire is shortened. On the other hand, the group (Ta) is a material whose dreaming speed is slower than that of the crane 4 320860 201022467 * material. There is also a method of forming a ruthenium film by using the button wire on a catalyst wire (for example, refer to Patent Document 2) 〇 Patent Document 1: Patent Document 1: Japanese Patent Laid-Open Publication No. 2003-303780, JP-A-2003-247062 SUMMARY OF THE INVENTION (Problems to be Solved by the Invention) However, when compared with tungsten, the mechanical strength of tantalum is low, especially when used in sorghum/JBL, the creep strength is low. Therefore, will
住變小、線阻抗變大而使線溫度上昇，而易於造成熔斷的 問題，以致未能提高良品率(生產性）。 雖然是說明以氮化硼（BN)被 同時，在專利文獻2中， 覆線表面的觸媒線，但氮化棚被覆並未能充分達成延長 鈕觸媒線的壽命’故期望可使其更為改善。 有鑑於上述的問題後，本發明即以提供可延長觸媒線 ❹壽命的觸媒化學氣相沉積裝置為課題。 、、 (解決問題的方法） 與本發明之〜形態相關的觸媒化學氣相沉積裝置是具 備··反應室、氣體導入源、觸媒線與加熱源。 一 上述氣體導入源係將原料氣體導入上述反應室中。 上述觸媒線是在钽線表面形成其硼化物層而成，且與 設置在上述反應室中的被處理基板相對向（相向）配置。 上述加熱源係加熱上述觸媒線。 【實施方式】 320860 5 201022467 與本發a月之一實施形態相關的觸媒化學氣相沉積襄置 是具備.反應室、氣體導入源、觸媒線與加熱源。 上述氣體導入源係將原料氣體導入上述反應室中。 上述觸媒線是在钽線表面形成其硼化物層而成，且與 設置在上述反應室中的被處理基板相對向（相向）配置。 上述加熱源係加熱上述觸媒線。 應用上述組成，因金屬钽的硼化物（硼化钽）比金屬钽 更為硬質，故可使用表面已形成有此硼化物層的鈕線作為 ® 觸媒線，以減低觸媒線的熱拉伸，而提高機械強度，進而 延長壽命。同時’應用上述組成，即可使其比钽線表面被 覆氮化硼或碳的觸媒線，更能延長壽命。 至於在组線表面形成獨化物層的方法，是將组線設置 於反應室中後’ 一邊將二蝴燒（B2He)氣體導入反應室内，〆 邊將钽線通電加熱。棚化物層的厚度並未特別限定，町藉 由钽線的加熱溫度、二硼统氣的氣體濃度、反應時間等適 ❹宜調整。 上述觸媒化學氣相沉積裳置，並且也可復具備由上述 加熱源以連續通電控制上述觸媒線的通電加熱之裝置。 應用上述組成，即可將表面已形成上述硼化物層的钽 線使用於觸媒線，將其通電加熱以進行成獏。此時，藉由 設置由連續通電以控制觸媒線的通電加熱之襞置，並在成 膜中持續進行觸媒線的通電加熱，而可緩和對於觸媒線的 熱休克（heat shock)，而抑制硼化物層產生龜裂，進而玎 延長觸媒線的壽命。 320860 6 201022467 . 以下，就本發明的實施形態參照圖面予以說明。 第1圖是應用於本發明的實施形態之觸媒化學氣相沉 積裝置的概略組成圖。觸媒化學氣相沉積裝置1具備已在 内部形成反應室2的真空腔3。在真空腔3連接著真空幫 浦4 ’可使反應室2真空排氣成所設定的真空度。反應室2 是形成在設置在真空腔3内部的防著板5之内方。 在以防著板5晝分成反應室2内部，設有數支的觸媒 ❹線6。觸媒線6是以鈕（Ta)線組成。在本實施形態中，數 支的觸媒線6是以將反應室2内部縱切於上下方向的方式 平行設置。再者，觸媒線6的設置形態並不限於上述的縱 方向，也可用將反應室2橫向橫切的形態設置。 每條觸媒線6是貫穿形成在防著板5的頂面及底面的 貝通孔5a、5b而設置，兩端部是連接在設置於真空腔3外 部的控制部8(控制裝置）。控制部8含有通電加熱觸媒線6 的加熱源。控制部8是藉由連續通電來進行觸媒線6之通 #電加熱者，而由電流供應源與調整供應電流的電腦等所組 成。 在反應室2内部’設有作為被成膜基材的基板5。基 板S可使用例如矩形的玻璃基板。在本實施形態中，如第 2圖所示，是以二片基板s挾持觸媒線6的方式予以相互 相對向配置。在此，是以基板S的長度方向垂直於觸媒線 6的延長方向之方式’將基板S設置於反應室2的内部。 而且，基板S是由未圖示的基板支撐裝置支撐。此基板支 撐裝置具有内建有將基板S加熱至所設定溫度的加熱源之 320860 201022467 結構。 防著板5大致為長方形狀，其四邊部分別設置氣體導 入配管7。由於氣體導入配管7是將原料氣體或二硼烷（B2h4) 氣體導入反應室2中的導管，故可透過氣體供應管線而連 接在已設於真空腔3外部的原料氣體供應部9a與二硼烷氣 體供應部9b。從氣體導入配管7喷出的原料氣體或二硼烷 氣體，主要疋導入二片的基板s之間。而且，由原料氣體 供應部9a與氣體導入配管7組成氣體導入源。 觸媒化學氣相沉積裝置i是以上述方式構成。接著， 針對使用此觸媒化學氣相沉積襞置丨的本實施形態的觸媒 化學氣相沉積方法加以說明。 (第1實施形態） 首先’啟動真空幫浦4將真空腔3的内部真空排氣後， 將反應室2減壓至所設定的真空度（例如lpa)。接著，在 從二硼烷氣體供應部9b將二硼烷氣體導入反應室2的同 ® 時，由控制部8將各觸媒線6通電後，加熱至所設定的溫 度（例如1’ 700°C)以上。此時，藉由觸媒線6的表面與二 硼烷氣體之接觸，而在觸媒線6的表面形成屬於反應生成 物的硼化钽層。When the residence becomes small and the line impedance becomes large, the temperature of the wire rises, which is liable to cause a problem of melting, so that the yield (productivity) cannot be improved. Although it is explained that boron nitride (BN) is simultaneously used, and in Patent Document 2, the catalyst wire on the surface of the covered wire is covered, but the nitriding shed is not sufficiently extended to extend the life of the button cell. More improved. In view of the above problems, the present invention has been made in an effort to provide a catalytic chemical vapor deposition apparatus which can extend the life of a catalyst strand. (Method for Solving the Problem) The catalytic chemical vapor deposition apparatus according to the aspect of the present invention is provided with a reaction chamber, a gas introduction source, a catalyst line, and a heating source. A gas introduction source introduces a material gas into the reaction chamber. The catalyst wire is formed by forming a boride layer on the surface of the twisted wire, and is disposed to face (opposing) opposite to the substrate to be processed provided in the reaction chamber. The heating source heats the catalyst line. [Embodiment] 320860 5 201022467 A catalytic chemical vapor deposition apparatus relating to one embodiment of the present invention is provided with a reaction chamber, a gas introduction source, a catalyst line, and a heating source. The gas introduction source introduces a material gas into the reaction chamber. The catalyst wire is formed by forming a boride layer on the surface of the twisted wire, and is disposed to face (opposing) opposite to the substrate to be processed provided in the reaction chamber. The heating source heats the catalyst line. With the above composition, since the boride of the niobium (barium boride) is harder than the niobium, the button wire on which the boride layer has been formed can be used as the ® catalyst line to reduce the heat pulling of the catalyst line. Stretch, and increase the mechanical strength, thereby extending the life. At the same time, by applying the above composition, it is possible to extend the life of the nitride wire or the catalyst line coated with boron nitride or carbon. As for the method of forming the individual layer on the surface of the group line, the group line is placed in the reaction chamber, and then the B2He gas is introduced into the reaction chamber, and the twist line is electrically heated. The thickness of the shed layer is not particularly limited, and the temperature is suitably adjusted by the heating temperature of the sputum line, the gas concentration of the diboron gas, and the reaction time. The catalyst chemical vapor deposition is carried out, and a device for controlling the energization heating of the catalyst wires by continuous energization by the above-mentioned heating source may be further provided. By applying the above composition, the ruthenium wire on which the above-described boride layer has been formed can be used for the catalyst wire, and it is electrically heated to be entangled. At this time, heat shock to the catalyst wire can be alleviated by providing a device for continuously controlling energization to control the energization heating of the catalyst wire, and continuing the energization heating of the catalyst wire during film formation. The inhibition of the boride layer causes cracking, thereby prolonging the life of the catalyst wire. 320860 6 201022467. Hereinafter, embodiments of the present invention will be described with reference to the drawings. Fig. 1 is a schematic configuration diagram of a catalytic chemical vapor deposition apparatus applied to an embodiment of the present invention. The catalytic chemical vapor deposition apparatus 1 is provided with a vacuum chamber 3 in which the reaction chamber 2 is formed inside. The vacuum chamber 4 is connected to the vacuum chamber 3 to evacuate the reaction chamber 2 to a set vacuum degree. The reaction chamber 2 is formed inside the prevention plate 5 provided inside the vacuum chamber 3. A plurality of catalyst strands 6 are provided inside the reaction chamber 2 so as to prevent the sheet 5 from being placed. The catalyst line 6 is composed of a button (Ta) line. In the present embodiment, a plurality of catalyst lines 6 are provided in parallel so that the inside of the reaction chamber 2 is longitudinally cut in the vertical direction. Further, the arrangement form of the catalyst wire 6 is not limited to the above-described longitudinal direction, and may be provided in a form in which the reaction chamber 2 is laterally transected. Each of the catalyst wires 6 is provided through the bead holes 5a and 5b formed on the top and bottom surfaces of the anti-plate 5, and both end portions are connected to a control unit 8 (control device) provided outside the vacuum chamber 3. The control unit 8 includes a heating source that energizes and heats the catalyst line 6. The control unit 8 is configured to perform the electric heater of the catalyst line 6 by continuous energization, and is composed of a current supply source and a computer that adjusts the supply current. Inside the reaction chamber 2, a substrate 5 as a film formation substrate is provided. The substrate S can use, for example, a rectangular glass substrate. In the present embodiment, as shown in Fig. 2, the two substrates s are opposed to each other so as to sandwich the catalyst wires 6. Here, the substrate S is placed inside the reaction chamber 2 such that the longitudinal direction of the substrate S is perpendicular to the direction in which the catalyst wires 6 extend. Further, the substrate S is supported by a substrate supporting device (not shown). The substrate supporting device has a structure of a built-in 320860 201022467 having a heating source for heating the substrate S to a set temperature. The anti-sliding plate 5 has a substantially rectangular shape, and gas guiding pipes 7 are provided at the four sides thereof. Since the gas introduction pipe 7 is a pipe for introducing a material gas or a diborane (B2h4) gas into the reaction chamber 2, it can be connected to the raw material gas supply portion 9a and the diboron which are provided outside the vacuum chamber 3 through the gas supply line. An a gas supply unit 9b. The material gas or diborane gas ejected from the gas introduction pipe 7 is mainly introduced between the two substrates s. Further, the material gas supply unit 9a and the gas introduction pipe 7 constitute a gas introduction source. The catalytic chemical vapor deposition apparatus i is constructed in the above manner. Next, a catalytic chemical vapor deposition method of this embodiment using this catalyst chemical vapor deposition apparatus will be described. (First Embodiment) First, the vacuum pump 4 is started to evacuate the inside of the vacuum chamber 3, and then the reaction chamber 2 is decompressed to a set vacuum degree (for example, 1 Pa). Next, when the diborane gas is introduced into the reaction chamber 2 from the diborane gas supply unit 9b, the control unit 8 energizes each of the catalyst lines 6 and then heats it to the set temperature (for example, 1'700°). C) above. At this time, a surface of the catalyst wire 6 is brought into contact with diborane gas to form a lanthanum boride layer which is a reaction product on the surface of the catalyst wire 6.
如上所述，由於表面上已形成硼化物層的钽線比金j 纽線更為硬質，故可因使用表面已形成有此魏物層的崔 線作為觸麟，而減少觸料6的熱伸長，使機械強度击 向’進而可延長壽命。再者，蝴化物層的膜厚度並 限定，可藉由组線的加熱溫度、二倾氣的氣㈣L 201022467 應時間等而適宜調整。 而且，關於在此钽線表面形成蝴化物層的步驟，可在 真空腔3的内部設置基板S之後再進行，也可在設置基板 S之前進行。此外，於不能設置二删燒氣供應管線的真空 腔中，也可移設其他已預先形成爛化物層的爛化物组觸媒 線。 接著’在停止導入二蝴烧氣之後’從原料氣體供應部 9a將原料氣體導入反應室2中。本實施形態中，是使用石夕 炫_(SiH〇氣體與氮氣（H2)的混合氣體作為.原料氣體，在基板 S的表面成膜矽（Si)膜。而且，形成在基板s表面之膜， ❿ 也可為使用碎院、氫氣及氨0H3)成膜的氮化碎（siN)膜、 使用三矽烷基胺（（SiHOW)、氨及氫氣成膜的氮化矽膜'、使 用六甲基二矽胺烷（（CHOdiNHSiKCH3)3,簡稱HMDS)成膜的 氮化矽膜、使用矽烷、氫氣及氧氣（〇〇或一氧化二氮（N2〇) 成膜的氧化矽（SiO)膜、使用矽烷與矽酸四乙酯 (SKOGH5)4，簡稱TE0S)成膜的氧化矽膜、使用矽烷、氫氣 與膦（ph3))或二硼烧成膜的摻磷石夕膜（n+Si膜）或推棚矽 膜（P + Si膜）、使用石夕院、氫氣與乙炔或甲淀成膜的碳化 石夕膜、使时烧與錯成膜的_膜、使用魏與六氣環氧 丙烧（簡稱鹏）成_聚四氟乙_續商標「純⑽」） 膜等。再者，在❹錢進錢化處理時，可達射膜的 膜去除自然氧化膜之目的。在使用氨氣進 盯氮化處理時，則可達成矽的氮化。 具體上，在基板S的成膜步驟中，是藉由控制部8將 320860 9 201022467 .直流電壓施加到觸媒線6後，對 。(：以上的高溫。而且，此時亦將基 加熱至例如1，7〇〇 度（例如大約300。〇。原料氣體板S加熱至所設定的溫 至互相對向配置的二片基板s之間從：體導入配管7導入 熱至高溫的觸媒線6上後，即可S。然後，在接觸到已加 應而生成的反應氣體之分解種在茂觸媒反應或熱分解反 此時，在以施加電流的開/關（上’冗積成膜。 ❹ 媒線6的通電加熱的情形中，因|Qn/〇ff)式運作進行觸 克（加熱而伸長或解除加熱而收縮）使觸媒線6受到的熱休 線6表面的龜裂，以致降低機械強声大而谷易引起觸媒 態中，在基板S成膜時，係藉由批 斤以，在本實施形 媒線6的通電加熱，一邊控制觸=彳部8 一邊連續進行觸 少觸媒線6受到熱休克。 、、6的加熱溫度，而減 至於應用控制部8控制觸媒線β、 續性地控制電流量將觸媒線6知執的通電方法，除了連 ❿ 法之外，還可舉出有以數階段進抒：：在所設定溫度的方 更方法UP/d_)。藉由㈣2線6的徐昇降壓變 寻方法，即可抑制形成在 觸媒線6表面的魏物層之龜裂發生，而提高機械的強度。 如上述，依據本實施形態，藉由將在表面已形成有硼 化物層的钽線予以使用在觸媒線6，即可減少觸媒線6的 熱伸長’並可提局機械強度及延長壽命之外，也可提高生 產力。而且，由於觸媒線是以鈕為主體的材料組成，故可 抑制與原料氣體之間產生合金化反應（矽化物化），而可獲 得穩定的成膜。 10 320860 201022467 . 再者，依據本實施形態，藉由在成膜中連續性進行觸 媒線6的通電加熱，可緩和觸媒線的熱休克、抑制表面硼 化物層的龜裂發生，並可延長觸媒線的壽命。第3圖A及 B是表面形成有硼化物層的觸媒線之側面SEM照片。第3 圖A是間歇性（以開/關操作）進行通電加熱時之例，明顯 出現表面龜裂的發生。又，第3圖B是連續性進行通電加 熱時之例，看不出表面龜裂的發生。 (第2個實施形態） ® 其次，說明應用於本發明第2個實施形態之觸媒化學 氣相沉積方法。 在反應室2的内部設置基板S與作為觸媒線6的鈕 線。然後，啟動真空幫浦4將真空腔3内部真空排氣後， 將反應室2減壓至所設定的真空度（例如IPa)。接著，透 過氣體導入配管7,使原料氣體及二硼烷氣體從原料氣體 供應部9a及二硼烷氣體供應部9b導入反應室2的同時， ❿由控制部8將各觸媒線6通電後，加熱至所設定的溫度（例 如1，700°C )以上。 此時，導入反應室2中的二硼烷氣藉由與觸媒線6接 觸、分解後，可在觸媒線6的表面形成硼化物（硼化鈕）層。 藉此，藉由觸媒線6表面硬化，可減少熱伸長，提高機械 強度，進而延長壽命。 另一方面，導入反應室2中的原料氣體藉由與觸媒線 6接觸、分解後，而使其反應生成物（分解種）沉積在基板S 的表面。因此，即可使石夕媒在基板S表面成膜。再者，由 11 320860 201022467 於原料氣體的分解種之分的蒸氣壓_⑻還低，故在收 的，塵環境及1，70(TC以上的高溫狀態中，該分解種不會 附著在觸媒線6上’或即使附著也立即蒸發。所以，石夕膜 不會沉積在觸媒線6表面，對於已形成在觸媒線6表面之 硼化物層不會有任何影響。 再者，在本實施形態中，也是由控制部8連續性進行 觸媒線6的通電加熱。藉此，即可抑制觸媒線6的硼化物 形成步驟及成膜步驟中觸媒線6表層龜裂之發生，而提高 觸媒線6的機械強度、耐久性，進而可望提昇良品率。 依據本實施形態時，可獲得與上述第1個實施形態同 樣的效果。尤其是應用本實施形態時，由於在對觸媒線表 面進行硼化物層形成步驟的同時，也可進行基板s的矽膜 成膜步驟，故更可提高其生產力。 [實施例] 使用不同組成的三種觸媒線進行Si的成膜試驗，並評 參估母種觸媒線的耐久性。其結果如第4圖所示。圖中，縱 軸為顯示器輸出（電壓值）’橫軸為累計膜厚。即，第4圖 是表示觸媒線的伸長與時間之關係。 實驗中使用的觸媒線是由加工成匚字形的直徑lmm、 長度3, 000mm的金屬钽線（純度99. 5%)組成的Ta觸媒線（試 料1)、已使上述鈕線表面爛化的B-Ta觸媒線（試料2)、已 將上述鈕線表面被覆氮化硼的BN-Ta觸媒線（試料3)。至 於觸媒線的通電方法’在試料1是間歇通電（開-關（ON-OFF) 通電）、在試料2是連續通電及間歇通電、在試料3是連續 320860 12 201022467 _ 通電。 試料2的初始硼化條件如下述。 [初始的硼化條件] 二领烧（B2H6)氣體流量：160sccm 施加電力：3Kw(顯示器電流值：約30A) 壓力：2Pa 成膜試驗的條件如下述。 [成膜試驗條件] ® 單矽烷（SiH4)氣體流量：32sccm 氫氣（H2)流量：16sccm 施加電力：3Kw(顯示器電流值：約30A) 壓力：2Pa 如第4圖所示，試料l(Ta觸媒線）是從開始成膜時即 急劇伸長直到斷裂。伸長率超過20%。 相對於此，試料2(B-Ta觸媒線）的耐久性就比試料1 Q 有大幅的提昇。尤其在連續通電時，從開始成膜即幾乎未 見到變形。另一方面，在間歇通電時，是從開始成膜慢慢 產生伸長直至最後斷裂。此即可認為是電流開、關時的熱 休克而使表面發生龜裂的原因。雖然其斷裂時的伸長已超 過10 %，但在财久性上是比試料1提高5倍以上。 其次，在試料3(BN-Ta觸媒線）方面，是從開始成膜慢 慢產生伸長直至最後斷裂。雖然斷裂時的伸長超過10%， 但在耐久性上是比試料1提高3倍以上。不過，在與試料 2的間歇通電時比較時，則耐久性較差。在與試料2的間 13 320860 201022467 歇通電時比較時的伸長變遷有差異，咸認為可能是其表面 硬度比試料2較低之故。 由以上的結果可知，鈕線表面已形成硼化物的觸媒線 (試料2)比起純钽線（試料1)及表面已形成氮化硼的觸媒 線（試料3)，可大幅提昇其耐久性。又，可確認是藉由連 續通電使觸媒線通電加熱，而抑制表面龜裂的發生，進而 可延長觸媒線的壽命。 以上，雖然是針對本發明的實施形態說明，但本發明 ® 並不侷限於此等形態的範圍，可根據本發明的技術性思考 作各種變形。 例如在以上的實施形態中，雖然在原料氣體是使用矽 烷與氫氣的混合氣體，但原料氣體並不侷限於此等氣體， 也可配合成膜材料的種類而作適度的變更。 再者，雖然在以上的實施形態中說明之例，是將二片 基板S對向配置在反應室2内部，並使數支觸媒線6縱向 φ 設置在此二片基板間，但反應室2的組成並不侷限於上述 之例。 更且，也可利用本發明的觸媒化學氣相沉積裝置，進 行太陽電池的P型層、N型層之成膜。 其中一例的太陽電池，首先是將由Mo膜等形成的金屬 電極，以濺鍍法或熱CVD法在玻璃、鋁等基板上成膜之後， 分別成膜為P型層（例如CuInSe2膜）、N型層（例如CdS膜） 後，再將ZnO等形成的透明電極在其上成膜後，即可製得 太陽電池。在此例中，可利用本裝置成膜為P型層的Cu I nSe2 14 320860 201022467 膜、N型層的CdS膜。 【圖式簡單說明】 第1圖係應用於本發明實施形態之觸媒化學氣相沉積 裝置的概略組成圖。 第2圖係第1圖中所示的裝置之反應室的概略斜視圖。 第3圖係表示設置在反應室中的觸媒線之表面狀態的 侧面圖（SEM)照片，A是表示已發生表面龜裂的狀態，B是 表示未發生表面龜裂的狀態。 第4圖係表示本發明實施例中說明的觸媒線之各種試 料的耐久性之圖。 【主要元件符號說明】 1 觸媒化學氣相沉積裝置 2 反應室 3 真空腔 4 真空幫浦 5 防著板 5a、 5b貫通孔 6 觸媒線 7 氣體導入配管 8 控制部 9a 原料氣體供應部 9b 二硼烷氣體供應部 S 基板 15 320860As described above, since the tantalum line on which the boride layer has been formed is harder than the gold j-line, the heat of the contact 6 can be reduced by using the Choi line on which the Wei layer is formed as a contact. Elongation, which causes the mechanical strength to hit 'and thus extend the life. Further, the film thickness of the butterfly layer is limited, and can be appropriately adjusted by the heating temperature of the line, the gas of the dip gas, the time of the 201022467, and the like. Further, the step of forming a wafer layer on the surface of the ridge line may be performed after the substrate S is provided inside the vacuum chamber 3, or before the substrate S is placed. Further, in the vacuum chamber in which the two purge gas supply lines cannot be disposed, other ruin group catalyst lines which have previously formed the ruin layer may be transferred. Then, the raw material gas is introduced into the reaction chamber 2 from the raw material gas supply portion 9a after the introduction of the two-boiler gas is stopped. In the present embodiment, a mixed gas of SiH〇 gas and nitrogen gas (H2) is used as a material gas, and a ruthenium (Si) film is formed on the surface of the substrate S. Further, a film formed on the surface of the substrate s is formed. , ❿ It can also be a sinter (siN) film formed by using a yard, hydrogen and ammonia 0H3), a tantalum nitride film formed using a trialkylamine ((SiHOW), ammonia and hydrogen film), using a hexameth a tantalum nitride film formed by a bismuthamine (CHOdiNHSiKCH3) 3, referred to as HMDS, a yttrium oxide (SiO) film formed by using decane, hydrogen, and oxygen (niobium or nitrous oxide (N2〇), A cerium oxide film formed by using decane and tetraethyl citrate (SKOGH5) 4 (referred to as TEOS), a phosphide film using decane, hydrogen and phosphine (ph3) or a diboron-forming film (n+Si film) ) or push the enamel film (P + Si film), use Shi Xiyuan, hydrogen and acetylene or methylated film to form a carbonized stone film, make the film and the film into a film, use Wei and Liu gas epoxy Propylene (referred to as Peng) into _ polytetrafluoroethylene _ continued trademark "pure (10)"). Moreover, when the money is processed into a money, the film of the film can be removed for the purpose of removing the natural oxide film. When ammonia is used for the nitriding treatment, cerium nitriding can be achieved. Specifically, in the film forming step of the substrate S, the DC voltage is applied to the catalyst line 6 by the control unit 8 after the DC voltage is applied to the catalyst unit 6. (The above high temperature. Moreover, at this time, the base is also heated to, for example, 1,7 Torr (for example, about 300 〇. The raw material gas plate S is heated to the set temperature to the two substrates s which are disposed opposite each other) From the introduction of the body introduction pipe 7 to the catalyst line 6 which is heated to a high temperature, it is possible to S. Then, in the contact with the decomposed species of the reaction gas which has been generated, the catalyst reaction or thermal decomposition is reversed. In the case of the on/off of the applied current (the upper part is formed by the filming of the medium), in the case of the electric heating of the medium 6 , the contact is performed by the operation of (Qn/〇ff) (heating and stretching or de-heating and shrinking) The crack of the surface of the heat line 6 received by the catalyst wire 6 is reduced, so that the mechanical sound is strong and the valley is easy to cause the catalyst state. When the substrate S is formed into a film, the film is used in the present embodiment. When the wire 6 is energized and heated, the contact with the crotch portion 8 is continuously subjected to heat shock. The heating temperature of 6, and 6 is reduced to the application control unit 8 to control the catalyst line β, and the control is continued. The electric current will know the energization method of the catalyst line 6, in addition to the ❿ method, it can also be cited Stage advancement:: The method of setting the temperature is UP/d_). By the method of (4) 2-line 6 Xu hoisting pressure change, the crack formation of the Wei layer formed on the surface of the catalyst wire 6 can be suppressed. Further, as described above, according to the present embodiment, by using the twisted wire having the boride layer formed on the surface on the catalyst wire 6, the thermal elongation of the catalyst wire 6 can be reduced. In addition to the mechanical strength and extended life, productivity can also be improved. Moreover, since the catalyst wire is composed of a button-based material, it can suppress the alloying reaction (deuteration) with the material gas, and can be stabilized. 10 320860 201022467 Further, according to the present embodiment, by energizing and heating the catalyst wire 6 continuously during film formation, heat shock of the catalyst wire can be alleviated, and cracking of the surface boride layer can be suppressed. Occurs and extends the life of the catalyst wire. Fig. 3A and B are SEM photographs of the side of the catalyst wire on which the boride layer is formed. Fig. 3A is intermittent (on/off operation) for energization heating In the case of time, there is a clear surface crack. Further, Fig. 3B shows an example in which the surface heating is continuously performed, and no occurrence of surface cracking is observed. (Second embodiment) ® Next, a catalyst applied to the second embodiment of the present invention will be described. Chemical vapor deposition method. A substrate S and a button wire as a catalyst wire 6 are disposed inside the reaction chamber 2. Then, the vacuum pump 4 is activated to evacuate the inside of the vacuum chamber 3, and then the reaction chamber 2 is depressurized to a position. The degree of vacuum (for example, IPa) is set, and the raw material gas and diborane gas are introduced into the reaction chamber 2 from the source gas supply unit 9a and the diborane gas supply unit 9b through the gas introduction pipe 7, and the control unit 8. After energizing each of the catalyst wires 6, the temperature is raised to a predetermined temperature (for example, 1,700 ° C) or higher. At this time, the diborane gas introduced into the reaction chamber 2 is contacted and decomposed by the catalyst wire 6. A boride (boron button) layer can be formed on the surface of the catalyst wire 6. Thereby, the surface of the catalyst wire 6 is hardened, whereby the heat elongation can be reduced, the mechanical strength can be improved, and the life can be prolonged. On the other hand, the material gas introduced into the reaction chamber 2 is brought into contact with the catalyst wire 6 to be decomposed, and the reaction product (decomposed species) is deposited on the surface of the substrate S. Therefore, it is possible to form a film on the surface of the substrate S. Furthermore, the vapor pressure _(8) of the decomposition of the raw material gas is still low by 11 320860 201022467, so the decomposed species will not adhere to the touch in the dusty environment and the high temperature state of 1,70 (TC or higher). The dielectric 6 is evaporating immediately or even if it is attached. Therefore, the stone film is not deposited on the surface of the catalyst wire 6, and has no influence on the boride layer which has been formed on the surface of the catalyst wire 6. Further, In the present embodiment, the control unit 8 also continuously performs energization heating of the catalyst wire 6. This can suppress the occurrence of surface cracking of the catalyst wire 6 in the boride forming step and the film forming step of the catalyst wire 6. In addition, the mechanical strength and durability of the catalyst wire 6 are improved, and the yield is expected to be improved. According to the present embodiment, the same effects as those of the first embodiment described above can be obtained. While the boride layer forming step is performed on the surface of the catalyst wire, the film forming step of the substrate s can also be performed, so that the productivity can be further improved. [Example] Si film formation is performed using three kinds of catalyst lines having different compositions. Test and evaluate the mother The durability of the catalyst wire is as shown in Fig. 4. In the figure, the vertical axis represents the display output (voltage value), and the horizontal axis represents the cumulative film thickness. That is, the fourth figure shows the elongation and time of the catalyst wire. The catalyst wire used in the experiment is a Ta catalyst wire (sample 1) consisting of a metal wire (purity of 99.5%) having a diameter of 1 mm and a length of 3,000 mm, which has been processed into a U-shape. B-Ta catalyst wire (sample 2) having a line surface rotified, BN-Ta catalyst wire coated with boron nitride on the surface of the button wire (sample 3). The method of energizing the catalyst wire is in sample 1 Intermittent energization (on-off (ON-OFF) energization), continuous energization and intermittent energization in sample 2, and continuous energization in sample 3: 320860 12 201022467 _ The initial boration conditions of sample 2 are as follows. [Initial boride Conditions] Two-burner (B2H6) gas flow rate: 160 sccm Applied power: 3 Kw (display current value: about 30 A) Pressure: 2 Pa The conditions of the film formation test are as follows. [Film formation test conditions] ® Monodecane (SiH4) gas flow rate: 32sccm Hydrogen (H2) flow: 16sccm Applied power: 3Kw (display current value: about 30A) Pressure Force: 2Pa As shown in Fig. 4, sample 1 (Ta catalyst line) is rapidly elongated from the start of film formation until breaking. The elongation exceeds 20%. In contrast, sample 2 (B-Ta catalyst line) The durability is much higher than that of the sample 1 Q. Especially in the case of continuous energization, almost no deformation is observed from the start of film formation. On the other hand, in the intermittent energization, the film is slowly elongated from the beginning to the end. This is considered to be the cause of cracking on the surface due to heat shock when the current is turned on and off. Although the elongation at break is more than 10%, it is more than five times higher than the sample 1 in terms of financial durability. Next, in the case of the sample 3 (BN-Ta catalyst line), the elongation from the start of film formation was delayed until the final fracture. Although the elongation at break was more than 10%, the durability was more than three times higher than that of the sample 1. However, when compared with the intermittent energization of the sample 2, the durability is inferior. There is a difference in the elongation transition when compared with the sample 2 between 13 320860 and 201022467. It is considered that the surface hardness may be lower than that of the sample 2. From the above results, it can be seen that the catalyst wire (sample 2) in which the boride is formed on the surface of the button wire can be greatly improved compared to the pure tantalum wire (sample 1) and the catalyst wire (sample 3) on which boron nitride has been formed. Durability. Further, it was confirmed that the catalyst wires were electrically heated by continuous energization, thereby suppressing the occurrence of surface cracks and further extending the life of the catalyst wires. The present invention has been described with respect to the embodiments of the present invention, but the present invention is not limited to the scope of the embodiments, and various modifications can be made in accordance with the technical scope of the present invention. For example, in the above embodiment, the material gas is a mixed gas of decane and hydrogen, but the material gas is not limited to these gases, and may be appropriately changed by the type of the film material. Further, in the above-described embodiment, the two substrates S are disposed opposite to each other in the reaction chamber 2, and the longitudinal direction φ of the plurality of catalyst lines 6 are disposed between the two substrates, but the reaction chamber is provided. The composition of 2 is not limited to the above examples. Further, it is also possible to form a film of a P-type layer or an N-type layer of a solar cell by using the catalyst chemical vapor deposition apparatus of the present invention. In one example of the solar cell, first, a metal electrode formed of a Mo film or the like is formed on a substrate such as glass or aluminum by sputtering or thermal CVD, and then formed into a P-type layer (for example, CuInSe 2 film) and N. After the type layer (for example, a CdS film), a transparent electrode formed of ZnO or the like is formed thereon to form a solar cell. In this example, the Cu I nSe 2 14 320860 201022467 film of the P-type layer and the CdS film of the N-type layer can be formed by the apparatus. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic view showing the configuration of a catalytic chemical vapor deposition apparatus according to an embodiment of the present invention. Fig. 2 is a schematic perspective view of a reaction chamber of the apparatus shown in Fig. 1. Fig. 3 is a side view (SEM) photograph showing the surface state of the catalyst wire provided in the reaction chamber, wherein A is a state in which surface cracking has occurred, and B is a state in which surface cracking has not occurred. Fig. 4 is a view showing the durability of various samples of the catalyst wires described in the examples of the present invention. [Explanation of main component symbols] 1 Catalyst chemical vapor deposition apparatus 2 Reaction chamber 3 Vacuum chamber 4 Vacuum pump 5 Anti-plate 5a, 5b through hole 6 Catalyst line 7 Gas introduction pipe 8 Control unit 9a Raw material gas supply unit 9b Diborane gas supply S substrate 15 320860