TW201404926A - Manufacturing method for photo-CVD film and manufacturing apparatus for photo-CVD film - Google Patents
Manufacturing method for photo-CVD film and manufacturing apparatus for photo-CVD film Download PDFInfo
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 68
- 238000006243 chemical reaction Methods 0.000 claims abstract description 123
- 238000000034 method Methods 0.000 claims abstract description 38
- 239000007789 gas Substances 0.000 claims description 135
- 239000000463 material Substances 0.000 claims description 46
- 230000005540 biological transmission Effects 0.000 claims description 31
- 239000000758 substrate Substances 0.000 claims description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 230000008569 process Effects 0.000 claims description 10
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 8
- 230000001678 irradiating effect Effects 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 15
- 238000007599 discharging Methods 0.000 abstract 2
- 239000010408 film Substances 0.000 description 187
- 238000005755 formation reaction Methods 0.000 description 22
- 230000015572 biosynthetic process Effects 0.000 description 20
- 238000009826 distribution Methods 0.000 description 16
- 239000011521 glass Substances 0.000 description 9
- 230000004888 barrier function Effects 0.000 description 7
- 230000003014 reinforcing effect Effects 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 238000005229 chemical vapour deposition Methods 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000011347 resin Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 4
- HMMGMWAXVFQUOA-UHFFFAOYSA-N octamethylcyclotetrasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 HMMGMWAXVFQUOA-UHFFFAOYSA-N 0.000 description 4
- 230000002265 prevention Effects 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- 230000006866 deterioration Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 229910052684 Cerium Inorganic materials 0.000 description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- UQEAIHBTYFGYIE-UHFFFAOYSA-N hexamethyldisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)C UQEAIHBTYFGYIE-UHFFFAOYSA-N 0.000 description 2
- 229940073561 hexamethyldisiloxane Drugs 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- WSPOQKCOERDWJQ-UHFFFAOYSA-N 2-methyl-1,3,5,7,2,4,6,8-tetraoxatetrasilocane Chemical compound C[SiH]1O[SiH2]O[SiH2]O[SiH2]O1 WSPOQKCOERDWJQ-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000005401 electroluminescence Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 description 1
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 230000009182 swimming Effects 0.000 description 1
- MZLGASXMSKOWSE-UHFFFAOYSA-N tantalum nitride Chemical compound [Ta]#N MZLGASXMSKOWSE-UHFFFAOYSA-N 0.000 description 1
- 229910001936 tantalum oxide Inorganic materials 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/48—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating by irradiation, e.g. photolysis, radiolysis, particle radiation
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/52—Controlling or regulating the coating process
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B33/00—Electroluminescent light sources
- H05B33/02—Details
- H05B33/04—Sealing arrangements, e.g. against humidity
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B33/00—Electroluminescent light sources
- H05B33/10—Apparatus or processes specially adapted to the manufacture of electroluminescent light sources
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- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
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Abstract
Description
本發明是有關光CVD膜的製造方法、及光CVD膜的製造裝置。 The present invention relates to a method for producing a photo CVD film and a device for producing a photo CVD film.
有機電致發光(以下有機EL)元件是具有低電力、自發光、高速應答等多的優點，朝平板顯示器(FPD)或照明機器的應用之開發正進展。並且，藉由使用樹脂基板(含樹脂薄膜)等的可撓性基板，產生彎曲、輕盈、不破裂等新的附加價值，朝有機EL元件的可撓性機器之應用也被檢討。 The organic electroluminescence (hereinafter, organic EL) element has advantages such as low power, self-luminescence, high-speed response, and the like, and development of applications to flat panel displays (FPD) or illumination devices is progressing. In addition, by using a flexible substrate such as a resin substrate (including a resin film), new added value such as bending, lightness, and no cracking is generated, and the application to a flexible device of an organic EL element is also reviewed.
有機EL元件一旦接觸於水分或氧，則會產生發光效率的降低或壽命劣化，因此必須從製造過程排除水分或氧。另一方面，就樹脂基板等的可撓性基板而言，必須抑制隨水分的吸收而產生的尺寸變動。基於以上的理由，有機EL元件是在其樹脂基板的表背形成勢壘膜。在此，所謂的勢壘膜是表示防止從外部進入至有機EL元件或樹脂基板的水分或氧之膜，為了抑制水分或氧的擴散，而使用膜密度大的薄膜。作為勢壘膜的具體的材料，可使 用矽氮化膜(以下稱「Si氮化膜」)或氧化鋁膜等。 When the organic EL element is exposed to moisture or oxygen, the luminous efficiency is lowered or the life is deteriorated, so it is necessary to remove moisture or oxygen from the manufacturing process. On the other hand, in the flexible substrate such as a resin substrate, it is necessary to suppress dimensional fluctuation due to absorption of moisture. For the above reasons, the organic EL element has a barrier film formed on the front and back of its resin substrate. Here, the barrier film is a film that prevents moisture or oxygen from entering the organic EL element or the resin substrate from the outside, and a film having a large film density is used in order to suppress diffusion of moisture or oxygen. As a specific material of the barrier film, A tantalum nitride film (hereinafter referred to as "Si nitride film") or an aluminum oxide film is used.
有機EL元件的密封膜是水分、氧的擴散防止為理所當然，還被要求(1)低溫成膜(有機EL劣化防止)，(2)低損傷(有機EL劣化防止)，(3)低應力、低楊式模數(剝落防止)，(4)高透過率(亮度劣化防止)等。對於此，上述的勢壘膜的各材料因為膜硬(楊式模數大)，且膜應力也大，所以一旦使用厚膜，會有膜剝落或龜裂發生的課題。 It is a matter of course that the sealing film of the organic EL element is prevented from diffusing moisture and oxygen, and (1) low-temperature film formation (organic EL deterioration prevention), (2) low damage (organic EL deterioration prevention), and (3) low stress, Low Yang modulus (peeling prevention), (4) high transmittance (lightness deterioration prevention), etc. In this case, since each of the above-described barrier films has a hard film (the Young's modulus is large) and the film stress is large, there is a problem that film peeling or cracking occurs when a thick film is used.
於是，作為有機EL元件的密封膜的構造，最受注目的是層疊薄膜構造。此為形成複數層目的不同的複數的薄膜之構造，有複數層疊勢壘膜及緩和勢壘膜的應力的薄膜(緩衝膜)之構造為人所知。在緩衝膜所被要求的項目是為了底層的平坦化或抑制附著於表面的異物的影響，而埋入性能佳、及膜軟(楊式模數小)膜應力小。作為緩衝膜的具體的材料，有含碳的矽氧化膜等。 Then, as a structure of the sealing film of the organic EL element, the most attention is paid to the laminated film structure. This is a structure in which a plurality of different thin films are formed for a plurality of layers, and a structure in which a plurality of stacked barrier films and a film (buffer film) for relieving the stress of the barrier film are known. The items required for the buffer film are for the purpose of flattening the underlayer or suppressing the influence of foreign matter adhering to the surface, and the embedding performance is good, and the film is soft (the Young's modulus is small) and the film stress is small. Specific materials of the buffer film include a carbon-containing tantalum oxide film and the like.
在專利文獻1是揭示有如此的層疊薄膜構造的密封膜。密封膜的製造方法是有電漿CVD法、光CVD法、濺射法、蒸鍍法等、各種成膜方法被提案，其代表例可舉：連續形成勢壘膜及緩衝膜之利用真空紫外光的光CVD法。 Patent Document 1 discloses a sealing film having such a laminated film structure. The method for producing a sealing film is a plasma film forming method such as a plasma CVD method, a photo CVD method, a sputtering method, or a vapor deposition method, and a representative example thereof is a vacuum ultraviolet ray which continuously forms a barrier film and a buffer film. Light photo CVD method.
光CVD膜的製造裝置是有專利文獻2及3。在專利文獻2的製造裝置中，原料氣體是從試料(被處理物)的橫方向導入。並且，在專利文獻3的製造裝置中是將試料上部的透過窗分割成複數，在各透過窗之間設置複 數的氣體導入口，藉此從試料的上方向導入原料氣體。 There are Patent Documents 2 and 3 for manufacturing a light CVD film. In the manufacturing apparatus of the patent document 2, a raw material gas is introduce|transduced from the horizontal direction of the sample (process object). Further, in the manufacturing apparatus of Patent Document 3, the transmission window at the upper portion of the sample is divided into a plurality of plural, and a complex is provided between the respective transmission windows. The number of gas introduction ports is used to introduce the material gas from the upper direction of the sample.
[專利文獻1]日本特開2005-63850號公報 [Patent Document 1] Japanese Patent Laid-Open Publication No. 2005-63850
[專利文獻2]日本特開2005-340702號公報 [Patent Document 2] Japanese Patent Laid-Open Publication No. 2005-340702
[專利文獻3]日本特開2012-12628號公報 [Patent Document 3] Japanese Patent Laid-Open Publication No. 2012-12628
一般的CVD裝置是具備原料氣體的導入機構、氣體排氣機構、自動壓力控制(APC)機構，用以下那樣的工程來形成光CVD膜。 A general CVD apparatus is provided with a material gas introduction mechanism, a gas exhaust mechanism, and an automatic pressure control (APC) mechanism, and a photo CVD film is formed by the following procedure.
(1)經由氣體導入閥來導入一定量的原料氣體至真空排氣後的反應室。 (1) A predetermined amount of raw material gas is introduced through a gas introduction valve to a reaction chamber after vacuum evacuation.
(2)調整APC閥，使壓力感測器設定成既定的壓力。 (2) Adjust the APC valve so that the pressure sensor is set to a predetermined pressure.
(3)點亮真空紫外光燈，開始光照射的成膜。 (3) The vacuum ultraviolet lamp is turned on, and film formation by light irradiation is started.
(4)一旦達既定的時間，則熄滅真空紫外光燈，將反應室真空排氣。 (4) Once the predetermined time has elapsed, the vacuum ultraviolet lamp is extinguished and the reaction chamber is evacuated.
在此，於工程(3)中是一面導入原料氣體，一面以反應室的氣體壓力能夠形成一定的方式控制排氣量。為此，在反應室存在氣流，亦即原料氣體的濃度分布。CVD 法的成膜速度是對氣體濃度也有依存性，因此為了使膜厚均一性提升，必須將氣體濃度分布形成均一。特別是在光CVD法中，因為原料氣體是在直接吸收光之下分解．反應，所以成膜速度是顯示對於氣體的流動或氣體濃度依存度大的傾向。 Here, in the item (3), the amount of the exhaust gas is controlled so that the gas pressure in the reaction chamber can be formed in a constant manner while introducing the material gas. For this purpose, there is a gas flow in the reaction chamber, that is, a concentration distribution of the raw material gas. CVD The film formation rate of the method is also dependent on the gas concentration. Therefore, in order to increase the uniformity of the film thickness, it is necessary to form a uniform gas concentration distribution. Especially in the photo CVD method, because the material gas is decomposed under direct absorption of light. Since the reaction rate is such that the film formation rate tends to be large depending on the flow of gas or the concentration of gas.
將如此的依存性的具體例顯示於圖7。圖7是表示像專利文獻2那樣在橫方向具有氣體導入口的光CVD膜的製造裝置中，在直徑300mm的試料形成光CVD膜時的膜厚均一性，尤其是顯示將原料氣體的供給量設為一定，僅改變反應室的氣體壓力時的膜厚均一性。由圖7可知，膜厚均一性會依氣體壓力而變動大。在圖8顯示以氣體壓力60Pa來成膜時的膜厚分布(%)。數值是表示對於試料內的平均膜厚的分布，對應於各個的等高線的間隔為2%的膜厚偏差。圖的箭號是表示試料上的原料氣體的流動方向。膜厚是顯示從氣體導入側(圖8的左下側)往排氣側(圖8的右上側)而變厚的傾向。如此，光CVD膜的膜厚是顯示對於原料氣體的流動或氣體濃度依存度大的特徵。 A specific example of such dependency is shown in FIG. In the apparatus for manufacturing a photo CVD film having a gas introduction port in the lateral direction as in Patent Document 2, the film thickness uniformity is formed when a sample having a diameter of 300 mm is formed into a photo CVD film, and in particular, the supply amount of the material gas is displayed. It is set to a certain value, and only the film thickness uniformity at the gas pressure of the reaction chamber is changed. As can be seen from Fig. 7, the film thickness uniformity varies greatly depending on the gas pressure. Fig. 8 shows a film thickness distribution (%) when a film is formed at a gas pressure of 60 Pa. The numerical value indicates the distribution of the average film thickness in the sample, and the film thickness deviation corresponding to the interval of each contour line was 2%. The arrow of the figure indicates the flow direction of the material gas on the sample. The film thickness tends to increase from the gas introduction side (lower left side in FIG. 8) to the exhaust side (upper right side in FIG. 8). As described above, the film thickness of the photo CVD film is characterized by a large dependence on the flow of the material gas or the gas concentration.
如此的成膜方法，例如若為像10mm×10mm等級那樣小尺寸的試料，則藉由氣體壓力的最適化或使試料旋轉，某程度也有確保膜厚的均一性的餘地。但，像第8代(2200mm×2500mm)的平板的玻璃基板那樣試料的尺寸變大，則僅壓力的最適化是難以確保膜厚的均一性。並且，使大型玻璃基板旋轉來成膜亦非現實性。 In such a film forming method, for example, a sample having a small size such as a size of 10 mm × 10 mm is used to optimize the gas pressure or to rotate the sample, and to some extent, there is room for ensuring the uniformity of the film thickness. However, when the size of the sample such as the glass plate of the 8th generation (2200 mm × 2500 mm) flat plate is increased, it is difficult to ensure the uniformity of the film thickness only by the optimization of the pressure. Moreover, it is also unrealistic to rotate a large glass substrate to form a film.
對於此，專利文獻3的光CVD膜的製造裝置是成為容易對應於更大型的玻璃基板之構造。在圖9顯示本案發明者針對專利文獻3記載的製造裝置之膜厚的場所依存性檢討後的結果。圖9是表示對於原料氣體的流動方向之膜厚分布的圖。原料氣體是從以一定的間隔所配置的G1~G5的上部來供給者。被供給至處理室的原料氣體是朝光之分解．反應進展的氣體的流動方向而成膜速度變大，但若氣體被消耗，則成膜速度變小。亦即，被成膜的膜厚是以氣體導入部作為基點，在氣體的流動方向形成正弦波那樣的分布。在圖9中是以細的實線來表示奇數號碼(G1、G3、G5)的氣體導入口之膜厚分布，以虛線來表示偶數號碼(G2、G4)的氣體導入口之膜厚分布。將細線及虛線加在一起的膜厚是以粗的實線所示的膜厚，成為實際的試料上的膜厚。亦即，若膜厚分布對於氣體的流動方向形成正弦波形狀的分布，則只要在其正弦波的半週期的位置設置氣體導入口，即便在大型玻璃基板中也可確保某程度的膜厚均一性。圖9是只顯示氣體的流動方向(X方向)的氣體導入位置(1次元表示)，但實際對於氣體的流動是在垂直方向(Y軸方向)也需要氣體的導入位置，因此氣體導入位置是形成設置一定的間隔之2次元的配置。 In this case, the apparatus for manufacturing a photo CVD film of Patent Document 3 is a structure that easily corresponds to a larger glass substrate. The results of the review of the site dependence of the film thickness of the manufacturing apparatus described in Patent Document 3 by the inventors of the present invention are shown in FIG. Fig. 9 is a view showing a film thickness distribution in a flow direction of a material gas. The material gas is supplied from the upper portion of G1 to G5 arranged at a constant interval. The material gas supplied to the processing chamber is decomposed toward light. The film formation speed in the flow direction of the gas in which the reaction progresses is increased, but if the gas is consumed, the film formation rate becomes small. In other words, the film thickness to be formed is a distribution in which a gas introduction portion is used as a base point and a sine wave is formed in the flow direction of the gas. In Fig. 9, the film thickness distribution of the gas introduction ports of the odd numbers (G1, G3, G5) is indicated by a thin solid line, and the film thickness distribution of the gas introduction ports of the even numbers (G2, G4) is indicated by a broken line. The film thickness in which the thin lines and the broken lines are added together is a film thickness indicated by a thick solid line, and becomes a film thickness on an actual sample. In other words, when the film thickness distribution forms a sinusoidal shape distribution in the flow direction of the gas, a gas introduction port is provided at a position of a half cycle of the sine wave, and a certain thickness uniformity can be ensured even in a large glass substrate. Sex. 9 is a gas introduction position (indicated by a dimension) showing only the flow direction (X direction) of the gas. However, the gas introduction position is required in the vertical direction (Y-axis direction). Therefore, the gas introduction position is A configuration in which a 2-dimensional arrangement of a certain interval is formed is formed.
如以上說明般，若根據像專利文獻3那樣從試料的上方向導入原料氣體之光CVD膜的製造裝置，則與像專利文獻2那樣從橫方向導入原料氣體之光CVD膜 的製造裝置作比較，可提升膜厚的均一性。然而，在專利文獻3所示的方法中，氣體導入口的配置會大大地左右膜厚均一性。亦即，因為需要從透過窗與透過窗之間導入氣體，所以在透過窗的形狀、大小、配置設限。換言之，專利文獻3的光CVD膜的成膜裝置會有只能在配合氣體導入位置的範圍檢討成膜條件的課題。 As described above, the light CVD film in which the material gas is introduced from the lateral direction as in Patent Document 2 is used as the apparatus for producing a photo CVD film in which the source gas is introduced from the upper side of the sample. The manufacturing device is compared to improve the uniformity of the film thickness. However, in the method disclosed in Patent Document 3, the arrangement of the gas introduction ports greatly increases the film thickness uniformity. That is, since it is necessary to introduce a gas from the transmission window and the transmission window, the shape, size, and arrangement of the transmission window are limited. In other words, the film forming apparatus of the photo CVD film of Patent Document 3 has a problem that the film forming conditions can be reviewed only in the range in which the gas introduction position is blended.
因此，需要即使像專利文獻2那樣從橫方向導入原料氣體也可提升膜厚的均一性，即使像專利文獻3那樣從試料的上方向導入原料氣體也可緩和氣體導入口的配置的限制之技術。有鑑於此，本案發明的目的是在於提供一種更容易提升膜厚的均一性之光CVD膜的製造方法或製造裝置。 Therefore, even if the material gas is introduced from the lateral direction as in the case of the patent document 2, it is necessary to improve the uniformity of the film thickness, and the technique of alleviating the arrangement of the gas introduction port by introducing the material gas from the upper side of the sample as in Patent Document 3 is required. . In view of the above, an object of the present invention is to provide a method and apparatus for producing a photo CVD film which is easier to increase the uniformity of the film thickness.
解決本案發明的課題之手段中代表性者，例如一種光CVD膜的製造方法的特徵係具有：(a)對形成光CVD膜的反應室導入光CVD膜的原料氣體，使反應室形成既定的壓力之工程；(b)在工程(a)之後，停止原料氣體導入至反應室、及原料氣體自前述反應室排氣，對反應室照射光之工程；及(c)在工程(b)之後，停止前述照射，然後將反應室排氣之工程， 重複複數次工程(a)~工程(c)。 A representative method for solving the problem of the present invention is, for example, a method for producing a photo CVD film, which comprises: (a) introducing a source gas of a photo CVD film into a reaction chamber in which a photo CVD film is formed, and forming a reaction chamber to be predetermined. (b) after the project (a), stopping the introduction of the raw material gas into the reaction chamber, and exhausting the raw material gas from the reaction chamber to illuminate the reaction chamber; and (c) after the project (b) , stopping the aforementioned irradiation, and then exhausting the reaction chamber, Repeat the multiple projects (a) ~ project (c).
或，一種光CVD膜的製造裝置，其特徵係具有：反應室，其係設置基板；光源部，其係從反應室的外部照射光；透過窗，其係使光朝反應室透過；第1氣體導入閥，其係朝反應室導入光CVD膜的原料氣體；第1排氣閥，其係被連接至反應室，將反應室排氣；及第2排氣閥，其係經由第1排氣閥來連接至反應室，將反應室排氣。 Or a manufacturing apparatus of a photo CVD film, comprising: a reaction chamber provided with a substrate; a light source unit that emits light from the outside of the reaction chamber; and a transmission window that transmits light toward the reaction chamber; a gas introduction valve that introduces a material gas of the photo CVD film into the reaction chamber; a first exhaust valve that is connected to the reaction chamber to exhaust the reaction chamber; and a second exhaust valve that passes through the first row A gas valve is connected to the reaction chamber to vent the reaction chamber.
或，一種光CVD膜的製造裝置，其特徵係具有：反應室，其係設置基板；光源部，其係從反應室的外部照射光；透過窗，其係使光朝反應室透過；第1氣體導入閥，其係朝反應室導入光CVD膜的原料氣體；複數的第1排氣閥，其係被連接至反應室，將反應室排氣；及第2排氣閥，其係經由複數的第1排氣閥來連接至反應室，直徑比前述複數的第1排氣閥更大。 Or a manufacturing apparatus of a photo CVD film, comprising: a reaction chamber provided with a substrate; a light source unit that emits light from the outside of the reaction chamber; and a transmission window that transmits light toward the reaction chamber; a gas introduction valve that introduces a material gas of the photo CVD film into the reaction chamber; a plurality of first exhaust valves that are connected to the reaction chamber to exhaust the reaction chamber; and a second exhaust valve that passes through the plurality of The first exhaust valve is connected to the reaction chamber and has a larger diameter than the plurality of first exhaust valves.
若根據本案發明，則提供一種更容易提升膜厚的均一性之光CVD膜的製造方法或製造裝置。 According to the invention of the present invention, there is provided a method and apparatus for producing a photo CVD film which is easier to increase the uniformity of the film thickness.
101、201、501‧‧‧反應室 101, 201, 501‧‧ ‧ reaction room
102、202、502‧‧‧試料基座 102, 202, 502‧‧‧ sample base
103、203、503‧‧‧試料(玻璃基板) 103, 203, 503‧‧‧ samples (glass substrate)
104、204、504‧‧‧透過窗(合成石英) 104, 204, 504‧‧ ‧ through the window (synthetic quartz)
105、205、505‧‧‧VUV燈 105, 205, 505‧‧‧VUV lamps
106、206、506‧‧‧原料氣體導入閥 106, 206, 506‧‧‧ raw material gas introduction valve
107、207、507‧‧‧反應室氣體壓力感測器 107, 207, 507‧‧‧ Reaction chamber gas pressure sensor
108、208、508‧‧‧排氣配管 108, 208, 508‧‧‧ exhaust piping
109、209、509‧‧‧排氣閥 109, 209, 509‧‧‧ exhaust valve
110、111、210、510‧‧‧APC閥 110, 111, 210, 510‧‧‧ APC valves
113‧‧‧氮氣導入閥 113‧‧‧Nitrogen introduction valve
114、214、514‧‧‧真空泵 114, 214, 514‧‧ ‧ vacuum pump
115、215‧‧‧補強框架 115, 215‧‧ ‧ reinforcement framework
圖1是表示實施例1的光CVD膜的製造裝置的圖。 Fig. 1 is a view showing a manufacturing apparatus of a photo CVD film of Example 1.
圖2是表示實施例1的光CVD膜的製造方法的圖。 FIG. 2 is a view showing a method of manufacturing the photo CVD film of Example 1. FIG.
圖3是表示光CVD膜的成膜速度對於反應室的壓力之依存性的圖。 Fig. 3 is a graph showing the dependence of the deposition rate of the photo CVD film on the pressure in the reaction chamber.
圖4是表示實施例2的光CVD膜的製造裝置的圖。 4 is a view showing a manufacturing apparatus of a photo CVD film of Example 2.
圖5是表示實施例3的光CVD膜的製造裝置的圖。 Fig. 5 is a view showing a manufacturing apparatus of a photo CVD film of Example 3;
圖6是表示實施例3的光CVD膜的製造方法的圖。 Fig. 6 is a view showing a method of producing a photo CVD film of Example 3;
圖7是說明有關光CVD膜的膜厚均一性的課題的圖。 FIG. 7 is a view for explaining a problem of film thickness uniformity of a photo CVD film.
圖8是說明有關光CVD膜的膜厚分布的課題的圖。 FIG. 8 is a view for explaining the problem of the film thickness distribution of the photo CVD film.
圖9是說明有關光CVD膜的膜厚分布的課題的圖。 FIG. 9 is a view for explaining a problem of a film thickness distribution of a photo CVD film.
圖10是表示藉由實施例1的製造方法來製造之光CVD膜的膜厚分布的圖。 FIG. 10 is a view showing a film thickness distribution of a photo CVD film produced by the production method of Example 1. FIG.
圖1是實施例1的光CVD膜的製造裝置的概要。裝置是由形成光CVD膜的反應室501、試料基座502、試料503、透過窗504、真空紫外光(VUV： Vacuum Ultraviolet)燈505、導入光CVD膜的原料氣體的原料氣體導入閥506、反應室壓力感測器507、用以從反應室排除原料氣體的排氣配管508、排氣閥509、自動壓力控制(APC)閥(APC：Auto Pressure Control)510、及真空泵514所構成，與專利文獻2所記載的光CVD膜的製造裝置同樣，原料氣體導入閥506對於試料503是處於橫方向。但，本實施例的發明是在光CVD膜的製造方法具有特徵，光CVD膜的製造裝置的構成並非限於此。與專利文獻3記載者同樣，藉由組合：對於試料503在上方向設置原料氣體導入閥的光CVD膜的製造裝置、及本實施例的光CVD膜的成膜方法，可更提升膜厚的均一性。本實施例是VUV燈505使用Xe2準分子燈(波長=172nm)，原料氣體使用有機矽來源的OMCTS(Octo methyl cyclotetrasiloxane)進行成膜。但，OMCTS為其一例，該等為合適例之一，並非限於此原料氣體。取得與OMCTS同樣效果的氣體，有TEOS(Tetra ethoxy silane)及氧、HMDSO(Hexa methyl disiloxane)等。另外，反應室501的壁及透過窗504，為了抑制反應物的附著，而加熱至120℃。另一方面，試料基座502的溫度是藉由冷卻器來控制於30℃。 Fig. 1 is an outline of a manufacturing apparatus of a photo CVD film of Example 1. The apparatus is a reaction chamber 501 in which a photo CVD film is formed, a sample base 502, a sample 503, a transmission window 504, a vacuum ultraviolet light (VUV: Vacuum Ultraviolet) lamp 505, a material gas introduction valve 506 that introduces a material gas of the photo CVD film, a reaction chamber pressure sensor 507, an exhaust pipe 508 for removing a material gas from the reaction chamber, an exhaust valve 509, an automatic pressure control (APC) valve (APC: Auto Pressure Control) 510, and a vacuum pump 514, and Similarly to the apparatus for manufacturing a photo CVD film described in Patent Document 2, the material gas introduction valve 506 is in the lateral direction with respect to the sample 503. However, the invention of the present embodiment is characterized by a method of manufacturing a photo CVD film, and the configuration of the apparatus for manufacturing a photo CVD film is not limited thereto. In the same manner as the one described in the patent document 3, the apparatus for manufacturing a photo CVD film in which the material gas introduction valve is provided in the upper direction of the sample 503 and the film formation method of the photo CVD film of the present embodiment can further increase the film thickness. Uniformity. In the present embodiment, the VUV lamp 505 is formed using a Xe 2 excimer lamp (wavelength = 172 nm), and the material gas is formed using OOCTS (Octo methyl cyclotetrasiloxane) derived from organic cerium. However, OMCTS is an example thereof, and these are one of suitable examples, and are not limited to this material gas. Gases having the same effects as OMCTS include TEOS (Tetra ethoxy silane), oxygen, and HMDSO (Hexa methyl disiloxane). Further, the wall of the reaction chamber 501 and the transmission window 504 were heated to 120 ° C in order to suppress the adhesion of the reactants. On the other hand, the temperature of the sample base 502 was controlled at 30 ° C by a cooler.
如上述般，在光CVD法中，成膜速度是對於原料氣體的流動或氣體濃度依存度大。相反而言，若無反應室內之原料氣體的導入或排氣所引起的流動，且氣體濃度分布均一，則成膜速度會形成均一。為了予以實現，只 要將氣體關閉於反應室的狀態下照射光即可。為此，藉由重複：將反應室內的壓力形成所望的壓力之工程、及在停止原料氣體的流動之狀態下進行所望的時間光照射之工程、以及進行真空排氣之工程，有助於形成光CVD膜的方法。 As described above, in the photo CVD method, the film formation rate is large in dependence on the flow of the material gas or the gas concentration. On the other hand, if the flow caused by the introduction or the evacuation of the material gas in the reaction chamber is not performed, and the gas concentration distribution is uniform, the film formation speed is uniform. In order to be realized, only It is only necessary to illuminate the light in a state where the gas is closed in the reaction chamber. For this reason, it is possible to repeat the process of forming the pressure in the reaction chamber to form the desired pressure, the process of performing the desired time light irradiation while stopping the flow of the material gas, and the vacuum evacuation process. A method of photo CVD film.
根據以上，將實施例1的光CVD膜的製造方法顯示於圖2。 From the above, the method for producing the photo CVD film of Example 1 is shown in Fig. 2 .
圖2的光CVD膜的製造方法的特徵是具有：(a)對形成光CVD膜的反應室導入光CVD膜的原料氣體，使反應室形成既定的壓力之工程；(b)在工程(a)之後，停止原料氣體導入至反應室、及原料氣體自反應室排氣，對反應室照射光之工程；及(c)在工程(b)之後，停止照射，然後將反應室排氣之工程， 重複複數次工程(a)~工程(c)。 The method for producing a photo CVD film of Fig. 2 is characterized in that: (a) a material gas for introducing a photo CVD film into a reaction chamber in which a photo CVD film is formed, and a process for forming a reaction chamber to a predetermined pressure; (b) engineering (a) After that, the process of introducing the raw material gas into the reaction chamber, exhausting the raw material gas from the reaction chamber, and irradiating the reaction chamber with light; and (c) stopping the irradiation after the engineering (b), and then exhausting the reaction chamber , Repeat the multiple projects (a) ~ project (c).
在圖10顯示藉由本實施例的製造方法來成膜之光CVD膜的膜厚分布。光照射時的氣體壓力是與圖8同樣設為60Pa。圖10所示的光CVD膜的膜厚的均一性與圖8作比較飛躍性地提升。如此，藉由進行本實施例的光CVD膜的製造方法，可飛躍性地提升光CVD膜的膜厚均一性。 The film thickness distribution of the photo CVD film formed by the manufacturing method of this embodiment is shown in FIG. The gas pressure at the time of light irradiation was set to 60 Pa in the same manner as in Fig. 8 . The uniformity of the film thickness of the photo CVD film shown in Fig. 10 is drastically improved as compared with Fig. 8. As described above, by performing the method for producing a photo CVD film of the present embodiment, the film thickness uniformity of the photo CVD film can be dramatically improved.
而且，若以本實施例的製造方法來進行光CVD膜的成膜，則不僅有膜厚均一性會提升的大優點， 且亦有緩和原料氣體的導入位置的限制，亦即透過窗的設置限制之優點。 Further, when the film formation of the photo CVD film is carried out by the production method of the present embodiment, not only the film thickness uniformity is greatly improved, but also the film thickness uniformity is improved. Moreover, there is also a limitation of easing the introduction position of the material gas, that is, the limitation of the setting of the transmission window.
並且，更適合的是以工程(a)的既定的壓力要比光CVD膜的成膜速度形成最大的壓力低為特徵。在光CVD法是按每種氣體，存在成膜速度形成最大之反應室的壓力。圖3是表示其情況，橫軸是反應室的壓力，縱軸是光CVD膜的成膜速度。例如在氣體種類A是約70Pa，在氣體種類B是約100Pa，具體的反應室的壓力是不同，但按每種氣體存在光CVD膜的成膜速度成為最大之反應室的壓力的點是共通。這是因為在光CVD膜的成膜反應中，原料氣體濃度的增大下分解．反應速度進展，成膜速度變大的成分、及原料氣體中的光吸收變大，到達試料基板的光減少，反應速度降低的成分共存所致。因此，一旦在成膜速度顯示最大值的壓力以上進行成膜，則原料氣體的使用效率會降低。其結果，在反應室內殘留未被使用於成膜反應的原料氣體，這會使透過窗朦朧，成為使反應效率降低的原因。因此，工程(a)的反應室的壓力是比此「光CVD膜的成膜速度成為最大的壓力」更低為佳。 Further, it is more preferable that the predetermined pressure of the process (a) is lower than the maximum pressure formed by the film formation speed of the photo CVD film. In the photo CVD method, the pressure of the reaction chamber which forms the maximum film formation rate for each gas is used. Fig. 3 shows the case where the horizontal axis represents the pressure of the reaction chamber and the vertical axis represents the film formation speed of the photo CVD film. For example, in the case where the gas type A is about 70 Pa and the gas type B is about 100 Pa, the pressure in the specific reaction chamber is different, but the point at which the film forming speed of the photo CVD film becomes the maximum in the reaction chamber of each gas is common. . This is because in the film formation reaction of the photo CVD film, the concentration of the material gas is increased to decompose. When the reaction rate is advanced, the component having a high film formation rate and the light absorption in the material gas become large, and the light reaching the sample substrate is reduced, and the component having a reduced reaction rate coexists. Therefore, when film formation is performed at a pressure higher than the maximum film formation rate, the use efficiency of the material gas is lowered. As a result, a raw material gas which is not used in the film formation reaction remains in the reaction chamber, which causes a transmission window to cause a decrease in reaction efficiency. Therefore, the pressure in the reaction chamber of the process (a) is preferably lower than the pressure at which the film formation rate of the photo CVD film becomes maximum.
如上述般在實施例1中是製造裝置的構成並無特別加以限定。然而，實施例1的光CVD膜的製造方法，可想像因為隨著多數次、高速開閉排氣側的閥之工程 (工程(a)及(c))，而在開閉時產生異物。於是，若製造裝置具有異物發生的抑制手段，則可更提升膜厚的均一化。在實施例2是基於以上情況說明可更提升膜厚的均一性之光CVD膜的製造裝置。 The configuration of the manufacturing apparatus in the first embodiment is not particularly limited as described above. However, the method of manufacturing the photo CVD film of the first embodiment is conceivable because the valve of the exhaust side is opened and closed at a high speed. (Engineering (a) and (c)), and foreign matter is generated during opening and closing. Therefore, if the manufacturing apparatus has a means for suppressing the occurrence of foreign matter, the uniformity of the film thickness can be further improved. In the second embodiment, a manufacturing apparatus of a photo CVD film which can further improve the uniformity of the film thickness will be described based on the above.
圖4是表示實施例2的光CVD膜的製造裝置的概要。圖4是具有2個大的排氣配管108及APC(APC：Auto Pressure Control)閥110、111之光CVD膜的製造裝置。裝置構成是由反應室101、試料基座102、試料103、透過玻璃104、真空紫外光(VUV：Vacuum Ultraviolet)燈105、原料氣體導入閥106、反應室壓力感測器107、排氣配管108、排氣閥109、第一APC閥110、第二APC閥111、第二APC閥用壓力感測器112、氮氣導入閥113、真空泵114所構成。透過窗104的材質是合成石英，分割成可維持機械強度的尺寸。在本實施例是設為短邊=200mm長邊=1500mm的長方形的透過窗104。在圖4是舉將透過窗104排列3片的構造(短邊方向)為例，但只要配合所使用的試料大小來增加透過窗104即可。例如，只要將此尺寸的透過窗排列10片，便可對應於第6代尺寸(1500mm×1850mm)的玻璃基板。在透過窗104與透過窗104之間是設置有保持透過窗104的補強框架115。補強框架115的寬是在充分維持機械強度且使光強度分布形成均一的基礎下，儘可能窄為理想。在本實施例，為了消除補強框架115的遮光部分的影響，而形成可使試料基座102運轉於2次元方向的構造。此運 轉寬是形成補強框架115的寬以上為理想。本實施例是使能夠在透過窗104的短邊方向以左右各50mm的間隔遊動。使試料基座102遊動的方向或遊動寬是只要考量透過窗104的形狀或補強框架115的寬來決定最適的值即可。 4 is a view showing an outline of a manufacturing apparatus of a photo CVD film of Example 2. 4 is a manufacturing apparatus of a photo CVD film having two large exhaust pipes 108 and APC (APC: Auto Pressure Control) valves 110 and 111. The apparatus configuration includes a reaction chamber 101, a sample base 102, a sample 103, a transmission glass 104, a vacuum ultraviolet light (VUV: Vacuum Ultraviolet) lamp 105, a material gas introduction valve 106, a reaction chamber pressure sensor 107, and an exhaust pipe 108. The exhaust valve 109, the first APC valve 110, the second APC valve 111, the second APC valve pressure sensor 112, the nitrogen introduction valve 113, and the vacuum pump 114 are formed. The material of the transmission window 104 is synthetic quartz, and is divided into dimensions capable of maintaining mechanical strength. In this embodiment, a rectangular transmission window 104 having a short side = 200 mm long side = 1500 mm is used. In FIG. 4, a structure (short side direction) in which three sheets are arranged in the transmission window 104 is taken as an example. However, the transmission window 104 may be added in accordance with the size of the sample to be used. For example, if the transmission window of this size is arranged in 10 sheets, it can correspond to the glass substrate of the 6th generation size (1500 mm × 1850 mm). A reinforcing frame 115 that holds the transmission window 104 is provided between the transmission window 104 and the transmission window 104. The width of the reinforcing frame 115 is preferably as narrow as possible while maintaining sufficient mechanical strength and uniformity of the light intensity distribution. In the present embodiment, in order to eliminate the influence of the light shielding portion of the reinforcing frame 115, a structure in which the sample base 102 can be operated in the second dimension direction is formed. This operation The widening is ideal for forming the width of the reinforcing frame 115 or more. In the present embodiment, it is possible to swim at intervals of 50 mm on the right and left sides in the short side direction of the transmission window 104. The direction in which the sample base 102 is swung or the width of the swimming is determined by taking into consideration the shape of the transmission window 104 or the width of the reinforcing frame 115 to determine an optimum value.
在此，說明圖4的製造裝置之光CVD膜的成膜方法。本構造的特徵是APC閥為以串聯2段所構成，前段的第一APC閥110是與反應室壓力感測器107連動，後段的第二APC閥111是與第二APC閥用壓力感測器112連動。第一APC閥110與第二APC閥111之間的配管是形成被導入經由氣體閥113來控制5流量的氮氣之構造。 Here, a film forming method of the photo CVD film of the manufacturing apparatus of FIG. 4 will be described. The present structure is characterized in that the APC valve is constituted by two stages in series, the first APC valve 110 in the front stage is interlocked with the reaction chamber pressure sensor 107, and the second APC valve 111 in the rear stage is sensed with the pressure of the second APC valve. The device 112 is linked. The piping between the first APC valve 110 and the second APC valve 111 is configured to be introduced into the nitrogen gas whose flow rate is controlled by the gas valve 113.
首先，打開氣體導入閥106來對反應室導入原料氣體的同時，以反應室壓力感測器107與第二APC閥用壓力感測器112能夠形成相同的壓力之方式輸出訊號。此時，打開氮氣用閥113來導入既定流量的氮氣。其次，一旦反應室101內形成既定的壓力，則關閉氣體導入閥106，開始光照射。此時，第一APC閥110的前後是控制成同壓力，因此反應室內的氣體的流動是停止。一旦既定的時間成膜，則關閉氮氣用閥113，將第一APC閥110及第二APC閥111全開而進行反應室101的抽真空。在重複此操作下，進行光CVD膜的成膜。圖4是以2段的串聯來表示APC閥，但當然亦可按照目的來增加段數。 First, the gas introduction valve 106 is opened to introduce the material gas into the reaction chamber, and the signal is outputted so that the reaction chamber pressure sensor 107 and the second APC valve pressure sensor 112 can form the same pressure. At this time, the nitrogen gas valve 113 is opened to introduce a predetermined flow rate of nitrogen gas. Next, when a predetermined pressure is formed in the reaction chamber 101, the gas introduction valve 106 is closed to start light irradiation. At this time, the front and rear of the first APC valve 110 are controlled to be the same pressure, and therefore the flow of the gas in the reaction chamber is stopped. When the film is formed at a predetermined time, the nitrogen gas valve 113 is closed, and the first APC valve 110 and the second APC valve 111 are fully opened to evacuate the reaction chamber 101. Under this operation, film formation of the photo CVD film was performed. Fig. 4 shows the APC valve in a series of two stages, but of course, the number of stages can be increased according to the purpose.
如此，本實施例的光CVD膜的製造裝置的特徵是具有： 反應室(101)，其係設置基板；光源部(真空紫外光燈105)，其係從反應室的外部來照射光；透過窗(104)，其係使前述光往反應室透過；第1氣體導入閥(106)，其係朝反應室導入光CVD膜的原料氣體；第1排氣閥(110)，其係被連接至反應室，將反應室排氣；及第2排氣閥(111)，其係經由第1排氣閥來連接至反應室，將反應室排氣。 Thus, the apparatus for manufacturing a photo CVD film of the present embodiment is characterized by having: a reaction chamber (101) for arranging a substrate, a light source portion (vacuum ultraviolet lamp 105) for illuminating light from outside the reaction chamber, and a transmission window (104) for transmitting the light to the reaction chamber; a gas introduction valve (106) that introduces a material gas of the photo CVD film into the reaction chamber; a first exhaust valve (110) that is connected to the reaction chamber to exhaust the reaction chamber; and a second exhaust valve ( 111), which is connected to the reaction chamber via a first exhaust valve, and exhausts the reaction chamber.
以下，說明該製造裝置的效果。如上述般，一旦開閉排氣閥，則在開閉時產生異物。特別是就基板大小為第8代等級的大型製造裝置而言，需要更大的排氣能力，必須縮小排氣系的氣導(conductance)。縮小排氣系的氣導之方法是有幾個方法，最一般的方法是擴大排氣配管或排氣系的主閥之方法。但，若急劇地多數次開閉該大的排氣閥，則異物發生的量也會變更多。 Hereinafter, the effects of the manufacturing apparatus will be described. As described above, when the exhaust valve is opened and closed, foreign matter is generated during opening and closing. In particular, in the case of a large-scale manufacturing apparatus having a substrate size of the eighth generation, a larger exhaust capability is required, and the conductance of the exhaust system must be reduced. There are several ways to reduce the air conduction of the exhaust system. The most common method is to expand the exhaust valve or the main valve of the exhaust system. However, if the large exhaust valve is opened and closed abruptly many times, the amount of foreign matter generated will also increase.
因此，最好採用可更抑制異物的發生之閥。舉在本實施例說明過的APC閥作為該閥的例子。由於APC閥是不像隔膜型閥那樣伴隨急速的開閉，因此即使擴大閥也可幾乎無異物的發生。但，APC閥在構造上是難完全停止排氣，通常的構成是難以使排氣氣體完全停止。 Therefore, it is preferable to use a valve which can suppress the occurrence of foreign matter more. The APC valve described in the embodiment is taken as an example of the valve. Since the APC valve does not open and close rapidly like a diaphragm type valve, even if the valve is enlarged, almost no foreign matter can be generated. However, the APC valve is structurally difficult to completely stop the exhaust gas, and it is generally difficult to completely stop the exhaust gas.
對於此，若根據本實施例的製造裝置，則藉由第1排氣閥及第2排氣閥的組合，可實質地停止反應室 內的氣體的流動。為此，第1及第2排氣閥可採用異物的發生較難的閥(例如APC閥)，與在實施例1說明過的製造裝置作比較，可更抑制異物的發生。在本實施例的製造裝置重要的點是光CVD膜的膜厚均一性完全不依靠原料氣體的導入位置，因此氣體閥的設置場所的自由度大，及膜厚均一性飛躍地提升。並且，藉由將難以完全關閉氣體的APC閥串聯地設置2段以上，可停止反應室的實質上的氣體的流動。因此，僅APC閥的動作，便可使排氣側的高速開閉動作成為可能，因此即使使用大型裝置，也可實現抑制處理能力的降低及異物的發生。 In this case, according to the manufacturing apparatus of the present embodiment, the reaction chamber can be substantially stopped by the combination of the first exhaust valve and the second exhaust valve. The flow of gas inside. Therefore, the first and second exhaust valves can be used as valves (for example, APC valves) which are difficult to generate foreign matter, and can suppress the occurrence of foreign matter as compared with the manufacturing apparatus described in the first embodiment. In the manufacturing apparatus of the present embodiment, the film thickness uniformity of the photo CVD film is completely independent of the introduction position of the material gas. Therefore, the degree of freedom in the place where the gas valve is installed is large, and the film thickness uniformity is drastically improved. Further, by providing two or more APC valves that are difficult to completely shut off the gas in series, the flow of the substantially gas in the reaction chamber can be stopped. Therefore, only the operation of the APC valve can make the high-speed opening and closing operation on the exhaust side possible. Therefore, even if a large-scale device is used, it is possible to suppress a decrease in the processing capability and the occurrence of foreign matter.
而且，本實施例的光CVD膜的製造裝置的特徵是更具有將氮氣導入至第1排氣閥及第2排氣閥之間的領域之第2氣體導入閥(113)。為了藉由該構成，使該領域與反應室形成等壓之下，可實質地停止反應室內的氣體的流動。 Further, the apparatus for manufacturing a photo CVD film of the present embodiment is characterized in that it further has a second gas introduction valve (113) that introduces nitrogen gas into the field between the first exhaust valve and the second exhaust valve. With this configuration, the field and the reaction chamber are formed under equal pressure, and the flow of the gas in the reaction chamber can be substantially stopped.
作為用以監控該領域及反應室的壓力之構成，更具有測定反應室的壓力之第1壓力感測器(107)、及測定該領域的壓力之第2壓力感測器(112)，第2氣體導入閥是只要以第2壓力感測器的測定值能夠與第1壓力感測器的測定值形成相等的方式來導入氮氣即可。 As a configuration for monitoring the pressure in the field and the reaction chamber, the first pressure sensor (107) for measuring the pressure of the reaction chamber and the second pressure sensor (112) for measuring the pressure in the field are provided. In the gas introduction valve, the nitrogen gas may be introduced so that the measured value of the second pressure sensor can be equal to the measured value of the first pressure sensor.
並且，藉由將第2排氣閥構成可根據來自第1壓力感測器的訊號進行控制，更容易將反應室內的壓力保持在適於成膜的壓力。 Further, by configuring the second exhaust valve to be controllable based on the signal from the first pressure sensor, it is easier to maintain the pressure in the reaction chamber at a pressure suitable for film formation.
如上述般，在本實施例的光CVD膜的製造裝置中，光CVD膜的膜厚均一性是不依靠原料氣體的導入位置。因此，可將第1氣體導入閥設在基板的橫方向。若依此配置，則與專利文獻3的光CVD膜的製造裝置作比較，可更降低透過窗或氣體導入口的限制條件，可使裝置設計的自由度提升。 As described above, in the apparatus for manufacturing a photo CVD film of the present embodiment, the film thickness uniformity of the photo CVD film is an introduction position that does not depend on the material gas. Therefore, the first gas introduction valve can be provided in the lateral direction of the substrate. According to this configuration, in comparison with the apparatus for manufacturing a photo-CVD film of Patent Document 3, the restriction conditions of the transmission window or the gas introduction port can be further reduced, and the degree of freedom in designing the device can be improved.
另外，在圖4所示的構造中，原料氣體導入閥106是僅顯示2處，但氣體導入閥106亦可為多數存在。同樣，氣體排氣閥109或APC閥110、111、及泵亦可多數存在。並且，在本實施例中是舉APC閥作為比隔膜型的閥還抑制異物的發生之閥的例子，但亦可採用其他的閥，只要是可奏效的閥。 Further, in the configuration shown in FIG. 4, only two places of the material gas introduction valve 106 are shown, but the gas introduction valve 106 may be present in a large number. Similarly, the gas exhaust valve 109 or the APC valves 110, 111, and the pump may be present in a large amount. Further, in the present embodiment, the APC valve is an example of a valve that suppresses the occurrence of foreign matter as a diaphragm type valve. However, other valves may be employed as long as they are effective valves.
實施例3是利用圖5及6來說明有關可更提升膜厚的均一性之光CVD膜的製造裝置中與實施例2不同者。 The third embodiment is different from the second embodiment in the apparatus for manufacturing a photo CVD film which can improve the uniformity of the film thickness by using FIGS. 5 and 6.
在圖5顯示本實施例的光CVD膜的製造裝置。圖5的光CVD膜的製造裝置是由反應室201、試料基座202、試料203、透過玻璃204、VUV燈205、原料氣體導入閥206、反應室壓力感測器207、複數的排氣配管208、複數的排氣閥209、APC閥210、及真空泵214所構成。在此，本實施例的製造裝置的特徵是經由複數的小排氣閥209來連接反應室201與APC閥210(排氣配管 208)的點。在本圖中是顯示並聯12個的排氣閥409之例。此12個的排氣閥409是形成全部同時開閉的構造，但並非限於此。並且，與實施例2同樣，透過窗204的材質是合成石英，顯示分割配置成可維持機械強度的尺寸之構造，為了消除補強框架215的遮光部分的影響，而將試料基座202形成可運轉於2次元方向的構造。 A manufacturing apparatus of the photo CVD film of this embodiment is shown in FIG. The apparatus for manufacturing a photo CVD film of FIG. 5 is a reaction chamber 201, a sample susceptor 202, a sample 203, a permeable glass 204, a VUV lamp 205, a material gas introduction valve 206, a reaction chamber pressure sensor 207, and a plurality of exhaust pipes. 208. A plurality of exhaust valves 209, an APC valve 210, and a vacuum pump 214 are formed. Here, the manufacturing apparatus of the present embodiment is characterized in that the reaction chamber 201 and the APC valve 210 (exhaust piping) are connected via a plurality of small exhaust valves 209. Point 208). In the figure, an example of 12 exhaust valves 409 in parallel is shown. The twelve exhaust valves 409 have a structure in which all of them are simultaneously opened and closed, but are not limited thereto. Further, in the same manner as in the second embodiment, the material of the transmission window 204 is synthetic quartz, and the structure in which the mechanical strength is divided and arranged is displayed, and the sample base 202 is made operable to eliminate the influence of the light shielding portion of the reinforcing frame 215. The structure in the 2 dimensional direction.
在本實施例也是VUV燈205為使用Xe2準分子燈(波長=172nm)，原料氣體為使用有機矽來源的OMCTS，進行成膜。反應室201的壁及透過窗204是設定成120℃，試料基座202的溫度是設定成30℃。在此是將反應室201的壁及透過窗204的溫度設為120℃，但當然亦可在能夠確保O型環的耐熱性的範圍設成更高。另外，加熱透過窗204的方法是有用細的加熱器線來直接加熱透過窗204的方法或加熱補強框架215的方法等。本實施例是加熱補強框架215，以其熱傳導來進行透過窗204的間接性的加熱。 In the present embodiment, the VUV lamp 205 is formed using a Xe 2 excimer lamp (wavelength = 172 nm), and the material gas is OMCTS using an organic cerium source. The wall of the reaction chamber 201 and the transmission window 204 were set to 120 ° C, and the temperature of the sample base 202 was set to 30 ° C. Here, the temperature of the wall of the reaction chamber 201 and the transmission window 204 is set to 120 ° C. However, it is of course possible to set the range of the heat resistance of the O-ring to be higher. Further, the method of heating the transmission window 204 is a method of directly heating the transmission window 204 by a thin heater wire or a method of heating the reinforcing frame 215. In this embodiment, the heat-reinforcing frame 215 is heated to perform indirect heating through the window 204 by heat conduction.
以下，說明本實施例的光CVD膜的製造方法。成膜時的製造流程是按照圖6所示的方法。首先，將玻璃基板203搬送至反應室201之後，把反應室201內真空排氣。接著，關閉排氣側的全部排氣閥(在本圖是記載12個)的同時，開啟氣體導入閥206來將OMCTS導入至反應室201。一旦反應室201的壓力開始上昇，則使試料基座202遊動。一旦反應室的壓力感測器(P1)207的壓力形成既定的壓力(例如70Pa)，則關閉原料氣體導入 閥206，點亮VUV燈205。一旦經過既定的時間，則熄滅VUV燈205的同時，將排氣閥209全開，把反應室201真空排氣。藉由重複以上的順序來形成所望的膜厚的光CVD膜。 Hereinafter, a method of manufacturing the photo CVD film of the present embodiment will be described. The manufacturing process at the time of film formation is in accordance with the method shown in FIG. First, after the glass substrate 203 is transferred to the reaction chamber 201, the inside of the reaction chamber 201 is evacuated. Next, all the exhaust valves on the exhaust side (12 in the figure) are closed, and the gas introduction valve 206 is opened to introduce the OMCTS into the reaction chamber 201. Once the pressure in the reaction chamber 201 begins to rise, the sample base 202 is allowed to swim. When the pressure of the pressure sensor (P1) 207 of the reaction chamber forms a predetermined pressure (for example, 70 Pa), the raw material gas introduction is turned off. Valve 206 illuminates the VUV lamp 205. Once the predetermined time has elapsed, the VUV lamp 205 is extinguished, the exhaust valve 209 is fully opened, and the reaction chamber 201 is evacuated. The photo-CVD film of the desired film thickness is formed by repeating the above sequence.
如此，本實施例的光CVD膜的製造裝置的特徵是具有：反應室(201)，其係設置基板；光源部(真空紫外燈205)，其係從反應室的外部照射光；透過窗(204)，其係使前述光朝反應室透過；第1氣體導入閥(206)，其係朝反應室導入光CVD膜的原料氣體；複數的第1排氣閥(209)，其係被連接至反應室，將反應室排氣；及第2排氣閥(210)，其係經由複數的第1排氣閥來連接至反應室，直徑比複數的第1排氣閥更大。 As described above, the apparatus for manufacturing a photo CVD film of the present embodiment is characterized in that the reaction chamber (201) is provided with a substrate, and the light source unit (vacuum ultraviolet lamp 205) irradiates light from the outside of the reaction chamber; 204), wherein the light is transmitted to the reaction chamber; the first gas introduction valve (206) introduces a material gas of the photo CVD film into the reaction chamber; and the plurality of first exhaust valves (209) are connected The reaction chamber is evacuated to the reaction chamber; and the second exhaust valve (210) is connected to the reaction chamber via a plurality of first exhaust valves, and has a larger diameter than the plurality of first exhaust valves.
依據該特徵，本實施例的光CVD膜的製造裝置也可取得與實施例2的製造裝置同樣的效果。亦即，被成膜的光CVD膜的膜厚均一性是完全不依靠原料氣體的導入位置，因此具有氣體閥的設置場所的自由度大、及膜厚均一性飛躍性地提升等的優點。 According to this feature, the apparatus for manufacturing a photo CVD film of the present embodiment can also obtain the same effects as those of the manufacturing apparatus of the second embodiment. In other words, since the film thickness uniformity of the film-formed photo-CVD film is completely independent of the introduction position of the material gas, there is an advantage that the degree of freedom of the place where the gas valve is installed is large, and the film thickness uniformity is drastically improved.
而且，若與實施例2作比較，則藉由複數配置小直徑的配管及閥，可同時實現小的氣導及異物發生的抑制。又，由於排氣閥小，所以可高速開閉動作，在本發 明的成膜方法中也可更擴大實質的成膜時間的比例。在此，對比圖2及圖6來說明實施例2及3的製造裝置的不同。圖2及圖6的不同是氣體排氣的停止及開始的速度的不同。圖2是平穩地進行氣體排氣閥的開閉速度的方法，相對的，圖6是使開閉速度陡峭的方法。如上述般，本實施例的光CVD膜的製造裝置是採用增加排氣的通過之構成作為縮小排氣系的氣導之手段。藉由如此縮小1個排氣配管的徑，使用複數的配管，可縮小排氣配管的總計的氣導。若排氣配管小，則小的隔膜閥的使用可能，因此本實施例的光CVD膜的製造裝置是即使進行高速的開閉動作，還是可更抑制異物的發生。另外，進行多數次開閉處理之小的隔膜閥的可靠度是在採用於原子狀CVD裝置(ALD-CVD法)已被證實。因此，排氣閥的組合是可使用能夠抑制異物的發生之隔膜閥作為複數的第1排氣閥，可使用APC閥作為第2排氣閥。 Further, in comparison with the second embodiment, by arranging a plurality of small-diameter pipes and valves, it is possible to simultaneously suppress the suppression of small air conduction and foreign matter. Moreover, since the exhaust valve is small, it can be opened and closed at a high speed. In the film forming method of the bright film, the ratio of the substantial film forming time can be further increased. Here, differences between the manufacturing apparatuses of the second and third embodiments will be described with reference to FIGS. 2 and 6. The difference between Fig. 2 and Fig. 6 is the difference in the speed at which the gas exhaust is stopped and started. FIG. 2 is a method of smoothly performing the opening and closing speed of the gas exhaust valve, and FIG. 6 is a method for making the opening and closing speed steep. As described above, the apparatus for manufacturing a photo CVD film of the present embodiment employs a configuration in which the passage of the exhaust gas is increased as means for reducing the air guide of the exhaust system. By reducing the diameter of one exhaust pipe as described above, it is possible to reduce the total air conduction of the exhaust pipe by using a plurality of pipes. When the exhaust pipe is small, the use of a small diaphragm valve is possible. Therefore, the apparatus for manufacturing a photo CVD film of the present embodiment can suppress the occurrence of foreign matter even if a high-speed opening and closing operation is performed. In addition, the reliability of a small diaphragm valve that performs a large number of opening and closing processes has been confirmed by the use of an atomic CVD apparatus (ALD-CVD method). Therefore, the combination of the exhaust valves can use a diaphragm valve that can suppress the occurrence of foreign matter as a plurality of first exhaust valves, and an APC valve can be used as the second exhaust valve.
另外，在本實施例是完全同時進行複數的排氣閥209的開閉，但亦可一點一點地錯開各個的閥的開閉時序，而使壓力不會急劇地變動。並且，在圖5是顯示2處原料氣體導入閥206，但實際原料氣體導入閥206是亦可複數存在。同樣，氣體排氣閥209也可以複數存在。 Further, in the present embodiment, the opening and closing of the plurality of exhaust valves 209 are performed at the same time, but the opening and closing timing of each valve may be shifted little by little, and the pressure does not suddenly fluctuate. In addition, in FIG. 5, the two raw material gas introduction valve 206 is shown, but the actual raw material gas introduction valve 206 may exist in plural. Similarly, the gas exhaust valve 209 can also be present in plural.
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| JP2012167922A JP2014027191A (en) | 2012-07-30 | 2012-07-30 | Manufacturing method of photo-cvd film and manufacturing apparatus of photo-cvd film |
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| JP6547271B2 (en) * | 2014-10-14 | 2019-07-24 | 凸版印刷株式会社 | Deposition method by vapor deposition on flexible substrate |
| JP6672595B2 (en) | 2015-03-17 | 2020-03-25 | 凸版印刷株式会社 | Film forming equipment |
| JP7175210B2 (en) | 2019-02-04 | 2022-11-18 | 東京エレクトロン株式会社 | Exhaust device, treatment system and treatment method |
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| JPS6212121A (en) * | 1985-07-10 | 1987-01-21 | Hitachi Ltd | Photo processing equipment |
| JPS63232416A (en) * | 1987-03-20 | 1988-09-28 | Sony Corp | Formation of thin-film through photochemical vapor growth |
| JPH04302138A (en) * | 1991-03-29 | 1992-10-26 | Furukawa Electric Co Ltd:The | Vapor growth device for semiconductor wafer |
| JPH04329626A (en) * | 1991-05-02 | 1992-11-18 | Matsushita Electron Corp | Processor of semiconductor device |
| JPH05251362A (en) * | 1992-03-06 | 1993-09-28 | Fujitsu Ltd | Low-pressure treatment device |
| DE69408405T2 (en) * | 1993-11-11 | 1998-08-20 | Nissin Electric Co Ltd | Plasma CVD method and device |
| JPH1011152A (en) * | 1996-06-26 | 1998-01-16 | Dainippon Screen Mfg Co Ltd | Vacuum exhaustion device of processor |
| JP2001060578A (en) * | 1999-08-20 | 2001-03-06 | Nec Corp | Vacuum treatment apparatus |
| US6930041B2 (en) * | 2000-12-07 | 2005-08-16 | Micron Technology, Inc. | Photo-assisted method for semiconductor fabrication |
| JP4644242B2 (en) * | 2007-12-10 | 2011-03-02 | 忠弘 大見 | How to use vacuum exhaust valve |
| JP2010087475A (en) * | 2008-09-03 | 2010-04-15 | Hitachi Kokusai Electric Inc | Method and device for manufacturing semiconductor device |
| US20100159122A1 (en) * | 2008-12-19 | 2010-06-24 | Canon Kabushiki Kaisha | Deposition film forming apparatus, deposition film forming method and electrophotographic photosensitive member manufacturing method |
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