TW200910426A - Silane free, plasma enhanced chemical vapour deposition of silicon nitride as an antireflective film and for hydrogen passivation of silicon wafer based photovoltaic cells - Google Patents

Silane free, plasma enhanced chemical vapour deposition of silicon nitride as an antireflective film and for hydrogen passivation of silicon wafer based photovoltaic cells Download PDF

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Publication number
TW200910426A
TW200910426A TW096131319A TW96131319A TW200910426A TW 200910426 A TW200910426 A TW 200910426A TW 096131319 A TW096131319 A TW 096131319A TW 96131319 A TW96131319 A TW 96131319A TW 200910426 A TW200910426 A TW 200910426A
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Taiwan
Prior art keywords
gaseous
feed material
wafer
silicon
silicon wafer
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TW096131319A
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Chinese (zh)
Inventor
Karin Kimes
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Reiser Hans Peter
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Publication of TW200910426A publication Critical patent/TW200910426A/en

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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
    • C23C16/22—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 deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/34—Nitrides
    • C23C16/345—Silicon nitride
    • 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
    • C23C16/50—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 using electric discharges
    • C23C16/511—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 using electric discharges using microwave discharges
    • 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
    • C23C16/50—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 using electric discharges
    • C23C16/515—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 using electric discharges using pulsed discharges
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/02—Details
    • H01L31/0216—Coatings
    • H01L31/02161—Coatings for devices characterised by at least one potential jump barrier or surface barrier
    • H01L31/02167—Coatings for devices characterised by at least one potential jump barrier or surface barrier for solar cells
    • H01L31/02168—Coatings for devices characterised by at least one potential jump barrier or surface barrier for solar cells the coatings being antireflective or having enhancing optical properties for the solar cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
    • H01L31/186—Particular post-treatment for the devices, e.g. annealing, impurity gettering, short-circuit elimination, recrystallisation
    • H01L31/1868—Passivation
    • 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
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
    • H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
    • H01L21/02123—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon
    • H01L21/0217—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon the material being a silicon nitride not containing oxygen, e.g. SixNy or SixByNz
    • 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
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
    • H01L21/02205—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition
    • H01L21/02208—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition the precursor containing a compound comprising Si
    • H01L21/02219—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition the precursor containing a compound comprising Si the compound comprising silicon and nitrogen
    • H01L21/02222—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition the precursor containing a compound comprising Si the compound comprising silicon and nitrogen the compound being a silazane
    • 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
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02225—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
    • H01L21/0226—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process
    • H01L21/02263—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase
    • H01L21/02271—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition
    • H01L21/02274—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition in the presence of a plasma [PECVD]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Sustainable Development (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Electromagnetism (AREA)
  • Inorganic Chemistry (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Plasma & Fusion (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Sustainable Energy (AREA)
  • Chemical Vapour Deposition (AREA)
  • Formation Of Insulating Films (AREA)

Abstract

A method to deposit a silicon nitride anti-reflective film by a silane-free plasma enhanced chemical vapour deposition process on silicon wafer based photovoltaic cells and to simultaneously passivate the silicon wafer by diffusion of hydrogen atoms through the surface of the silicon wafer. In a typical embodiment as shown in Fig.2 silicon, nitrogen and hydrogen containing gaseous or vaporous feedstock materials are introduced in a vacuum vessel 10 by distribution systems 11 and 12. A plasma source 5, supplied with high frequency electromagnetic power, preferably pulsed microwave power, ignites a plasma discharge 6 under suitable vacuum conditions. A silicon nitride film 2 will form on the hot, semi-finished silicon wafer 3 based photovoltaic cells 7 attached to a carrier and heating stage 8 while hydrogen atoms diffuse into the silicon wafer to passivate dangling bonds. It is advantageous that the silicon containing feedstock material is not silane but an organo-silicon compound such as hexamethyldisilazane.

Description

200910426 九、發明說明： 【發明所屬之技術領域】 本發明乃關於真空化學氣相沉積之系統與方法。 【先前技術】 典型之基於矽晶圓之光伏電池截面係如圖丨所示。矽 晶圓（光伏電池之光吸收物）3係加以摻雜，以使p_n接合可 形成。入射光將被晶圓所吸收，且電子-電洞對可藉光子能 量的轉化以建立。藉由p_n接合所產生的電場將強迫電子 與電洞以相反的方向向晶圓表面傳送。電子係藉後電極4 以收集，而前電極！則藉將電子注入摻雜的矽晶圓3的表 面以中和電洞。雖然後金屬電極通常會覆蓋整個晶圓表 面’但金屬前電極通常具有柵格結構以允許光線穿透晶圓 表面。 前與後電極可藉電負荷連接以形成電路，且當光伏電 池曝露於光線下時電流將可流動。介於以圓3表面盘前 電極1間的抗反射層2 @目的係降低從石夕晶圓表面反射的 光線。此層使發亮的類似今凰本 J頌似金屬表面的光學外觀轉變成深藍 色。通常抗反射層必須從例如為氧化物與_的透光物 質製造’且此層的厚度需根據其折射率選擇，以使光學厚 度符合入射光譜特定波長的四分一 刀之一。在抗反射層沉積前 或過程中，氫原子必須擴散進 令日日圓录面’以將石夕晶圓 晶格内的矽原子的懸空鍵加 ^入 埏加以飽和。此需要光伏電池在通 常介於200與400°C的冥加π χ 刃阿姐下。未經此鈍化，這些未飽 原子鍵將成為導電帶内的雷工 的電子的困陷位置。被困陷住的電 200910426 子將從光伏電流中損失，且會使光伏電池效率退化。在抗 反射層沈積且氫鈍化後，將前電極柵格！沉積在抗反射層 2上。前電極柵格與矽晶圓間的電導係藉隨後將整個光伏 電池曝露於高溫環境以達成，㈣謂的燒成步驟邮叫 step)。 現今之技術係藉施加-適當之方法，以在抗反射層的 沈積過程中達切晶圓之氫鈍化。在富含氫原子的環境 中，通:可接受使用基於真空電漿的氮化石夕沈積方法。 目前主要有二種不同的真空雷％ hi方去可用於形成氮化 W m . a.固態石夕革巴的陰極侵蚀(濺射）：使用氬氣用於電漿形 赫的範圍)、或射頻能量的形式供應:b k爷，沈積逮率隨頻率的提高而降低 b_電聚增強的化學氣相沉積(CVD) 炫（化學式siH作切_的進料物質，1夕 氣作為原子氮與氫的來源。在電漿中進料物質用風 能量係以射頻、特高頻或微波能量的方式件應:需的 積速率係隨頻率的提高而升高。 ，'、通㊉，沈 併:學氣相沈積（CVD)是一種藉氣相或汽相 貝—起反應形成薄臈以在基材 b于物 ⑽所使用的氣體或蒸汽係含有欲沉積;積相的方法。 或其他氣體反應以沉積薄膜的元素或:素且 B月b基的氣體 200910426 或化合物。CVD反應可以熱觸發、電漿引發、電裝增強戍 藉光子誘發系統内的光線以觸發。 作為矽與氫的來源且無其他不欲原子種類的妙燒氣體 是一種易分解且高反應性的化合物，從高沈積速率來看是 理想的。但矽烧的主要優點（其反應性）亦是明顯的缺點。 虽在至溫下與空軋接觸時’石夕烧氣體將會在無需任何額外 能量供應下自發性地燃燒。此使矽烷非常具有危險性，且 在製造環境中難以處理。為了將矽烷氣體儲存、供應至cvD 反應器且從CVD反應器排出廢氣，將需要複雜且昂貴的 安全裝置。與像是使用固態矽的基於陰極侵蝕方法的其他 方法相比，用於安全措施的額外費用是基於CVD的氮化 矽形成方法的明顯缺點。此是為何本發明、一種用於氮化 矽抗反射塗層沉積且同時加以氫鈍化的無矽烷之方 法將是邁向降低結晶光伏電池製造費用的一大步。 【發明内容】 一種無矽烷之電漿增強化學氣相沈積方法以在基於矽 晶圓之光伏電池上沉積氮化矽抗反射薄膜，且同時藉氫原 子擴散通過石夕晶圓表面以鈍化石夕晶圓。 在圖2中所示的典型具體實例中’含有矽、氮與氫的 ^態或汽態進料物質係藉分配系統n與12以飼入真空容 =10中。供應以高頻電磁能量（較佳係脈衝微波能量）的電 漿來源5將在適當的真空條件下點燃電漿放電6。氮化矽 ^膜2將會在放置於搬運與加熱平台8上的基於高溫、半 完成之梦晶圓3的光伏電池7上形成，同時氫原子擴散進 200910426 入矽晶圓内以鈍化懸空鍵。其優點為含矽之進料物質並非 矽烷，而是例如為六甲基二矽氮烷之有機矽化合物。 【實施方式】 ^产將基於半完成矽晶圓之光伏電池7(如圖丨中所示、但 热氮化矽層2與前接觸柵格1)裝入真空容器1〇内，且放 置在搬運與加熱器平台8上。在容器内的殘留氣體壓力必 須足夠低，以避免主要是氧來污染所沉積的薄膜。在操作 週期之間，容器的頻繁排氣因此應避免。 +刼作週期係藉由氣體分配系統丨丨與12以將進料氣體 或瘵汽飼入容器以起始。含矽之進料分配系統丨丨較佳係 位於光伏電池7與電槳來源5間，且所有其他的氣態進料 物質係藉位於電槳來源5相反側的另一個進料分配系統Η 以飼入。當然，所有必需的進料物質亦可藉單一分配系統 以飼入’但然、後電漿來源、5將經歷通常為非所欲之自我塗 2田所有進料氣體流動在用於非磁化CVD的適當壓力（通 书介於 0.05 至 lhPaP气、 王1 iih間）下已穩定時，且搬運與加熱器平台 8已將光伏電池加熱至所欲之溫度（通常介於肖伽c 間’取決於方法與矽晶圓物質)後，在電聚來源5處的電漿 放電6將藉適當能量來源所供應的電力或電磁能量以點 燃。在薄膜形成期間，亦可能連續地將光伏電ί也7移入薄 膜形成區域内以及再次地移出。 / 較U選擇例如為245〇 ΜΗζ的非常高電磁頻率的能 置〜因為可造成高薄膜沈積速率的高電漿密度是理想 的。糟分配系& 12所飼人的氣態或汽態非含料料物質 200910426 在向真空栗抽口 9、9,移動過程中將通過電漿區域6。在電 製區域中，進料分子將取決於與電漿粒子或電漿輻射交互 作用的類型而被解離、自由 田丞化 '激化、或離子化。進料 分子的特定部份在向光伏…與真空泵抽口 9、9,移動 時將呈能量激發狀態；後者位置可如圖2所示，但亦可位 於搬運與加熱平台8後方。 藉分配系統11所飼入的含矽之進料物質亦將朝向真空 9 9移動。由於含⑦分子並不通過電漿區域，故 其係藉《輻射以及藉與能量激發之含氮進料分子的交互 作用以激發且^解1切晶圓表面的各種能量激發之成 2將形成氮化㈣膜’且將氫原子提供給梦晶圓以純化懸 工鍵不過，飼入含矽進料物質的精確位置可取決於一般 之方法條#、所欲之沈積速率與例如為石炭的其他原子在抗 反射薄膜内的允許量。可能因此必須將含石夕㈣物質直接 暴露於電漿。 由於此專利申請案的發明性係在於以例如為六甲基二 石夕氮烧（化學式（CH3)3-Si-NH-Si-(CH3)3)的有機碎化合物來 取代矽烷氣體，故個別分子的有效裂解與同時抑制碳原子 包含進入抗反射薄膜内將是重要的。藉電漿放電所造成的 分子裂解程度主要取決於電聚電子溫度、電毁密度盥來自 電漿的真空紫外線㈣強度。裂解較佳應使碳仍維持或形 成揮發性烴類化合物，其最後可藉真空泵抽口 7 3以從 製程區域中排出。 含矽氣體進料物質與其餘進料物質間的流量比值通常 200910426 應加以設定，以使化學計量的氣化石夕（化學式w#4)可以形 成。不過，不同類型的基於石夕的光伏電池將需要對氣化石夕 組成加以調整。所有調整的目標在使光伏電池的效率最大 化。當含石夕與氮的進料物質的氫含量不足以充份純化石夕晶 圓時，可將分子氫加入至此電藏方法中。 為了達成高沈積速率、進料物質的適當分子裂解程度、 以及提高沈積方法的空間均勻性，電漿來源5可以提供以 微波能量（較佳係2450 MHz)且可以脈衝模式操作。較佳之 矩形脈衝之尖峰高度較佳應係較會導致可接受之沉積薄膜 結果的相當之連續波程度者高數倍（例如5倍）。開脈衝對 關脈衝的比值應設定成尖峰功率比值的倒數。 如圖2中所示的電漿來源5與進料物質分配系統η、 12可以安裝在光伏電池7的上方或下方。搬運與加熱平台 8需要據此加以調整。 【圖式簡單說明】 圖1係描述基於矽晶圓之光伏電池之截面。其基本上 係由作為光吸收物的摻雜矽晶圓3、後電極4、前電極撕 格1與抗反射薄膜2所組成。 圖2係說明一用於藉電漿增強化學氣相沈積法以在基 於石夕晶圓之光伏電池上沉積抗反射薄膜的反應器之—實 例。反應器係由真空容器10、放置在搬運與加熱平台8上 的光伏電池7、具有電漿6的電漿來源5、泵抽口 9、9,與 進料物質分配系統11與12所組成。 【主要元件符號說明】 200910426 1 前電極 2 氮化矽薄膜（抗反射層） 3 換雜的碎晶圓 4 後電極 5 電漿來源 6 電漿放電 7 光伏電池 8 搬運與加熱平台 9 真空泵抽口 9， 真空泵抽口 10 真空容器 11 進料物質分配系統 12 進料物質分配系統 12200910426 IX. INSTRUCTIONS: TECHNICAL FIELD OF THE INVENTION The present invention relates to systems and methods for vacuum chemical vapor deposition. [Prior Art] A typical wafer-based photovoltaic cell cross-section is shown in FIG.晶圆 The wafer (light absorber of the photovoltaic cell) 3 is doped so that p_n bonding can be formed. The incident light will be absorbed by the wafer, and the electron-hole pair can be converted by photon energy. The electric field generated by the p_n junction forces the electrons and holes to travel in opposite directions toward the wafer surface. The electrons are borrowed from the rear electrode 4 to collect, while the front electrode! Then, electrons are injected into the surface of the doped germanium wafer 3 to neutralize the holes. Although the back metal electrode typically covers the entire wafer surface, the metal front electrode typically has a grid structure to allow light to penetrate the wafer surface. The front and rear electrodes can be connected by an electrical load to form an electrical circuit, and the current will flow when the photovoltaic cell is exposed to light. The anti-reflection layer 2 @ between the electrodes 1 in front of the disk of the circle 3 is intended to reduce the light reflected from the surface of the stone wafer. This layer transforms the optical appearance of a shiny metal-like surface into a dark blue color. Typically the antireflective layer must be fabricated from a light transmissive material such as oxide and Å and the thickness of this layer is selected according to its refractive index such that the optical thickness conforms to one of the quarter-knife of the particular wavelength of the incident spectrum. Before or during the deposition of the anti-reflective layer, the hydrogen atoms must diffuse into the sundial recording surface to saturate the dangling bonds of the helium atoms in the crystal lattice of the Shixi wafer. This requires a photovoltaic cell that is usually between 200 and 400 °C. Without this passivation, these unsaturated atomic bonds will become trapped locations for the electrons of the Rays in the conductive strip. The trapped electricity 200910426 will be lost from the photovoltaic current and will degrade the efficiency of the photovoltaic cell. After the anti-reflective layer is deposited and hydrogen is passivated, the front electrode grid is placed! It is deposited on the anti-reflection layer 2. The conductance between the front electrode grid and the tantalum wafer is achieved by subsequently exposing the entire photovoltaic cell to a high temperature environment. (4) The so-called firing step is called step). Today's technology employs a suitable method to achieve hydrogen passivation of the wafer during deposition of the antireflective layer. In an environment rich in hydrogen atoms, it is acceptable to use a vacuum plasma-based nitriding deposition method. At present, there are mainly two different kinds of vacuum ray, which can be used to form nitriding W m . a. Cathodic erosion (sputtering) of solid Shishigeba: using argon for the range of plasma shape), or In the form of RF energy supply: bk, the deposition rate decreases with increasing frequency. b_Electrical polymerization enhanced chemical vapor deposition (CVD) Hyun (chemical formula siH for cutting_feeding material, 1 气 as atomic nitrogen and The source of hydrogen. In the plasma, the material used in the plasma is based on radio frequency, ultra-high frequency or microwave energy. The required product rate increases with the increase of frequency. ', 通十, sink and : Vapor deposition (CVD) is a method in which a gas or vapor phase is formed by gas phase or vapor phase reaction to form a thin gas to be deposited on a substrate b in a material (10); a method of depositing phase; or other gas The reaction is to deposit the elements of the film or the gas and the compound of the B-substrate 200910426 or the compound. The CVD reaction can be triggered by thermal triggering, plasma-induced, and electrical-enhanced light-induced photons in the system to act as a source of helium and hydrogen. And there is no other burning gas that does not want atomic species is an easy decomposition Highly reactive compounds are ideal from a high deposition rate. However, the main advantage of the calcination (the reactivity) is also a significant disadvantage. Although it is in contact with the air rolling at the temperature, the stone gas will be It spontaneously burns without any additional energy supply. This makes decane very dangerous and difficult to handle in the manufacturing environment. In order to store and supply decane gas to the cvD reactor and exhaust the effluent from the CVD reactor, it will be complicated. And an expensive safety device. The additional cost for safety measures is a significant disadvantage of the CVD-based tantalum nitride formation method compared to other methods such as the cathode erosion method using solid helium. This is why the present invention, a The method for decane-free deposition of tantalum nitride anti-reflective coating and hydrogen passivation at the same time will be a major step toward reducing the manufacturing cost of crystalline photovoltaic cells. SUMMARY OF THE INVENTION Plasma-enhanced chemical vapor deposition without decane Method for depositing a tantalum nitride antireflective film on a silicon wafer based photovoltaic cell while simultaneously diffusing through the surface of the stone wafer by hydrogen atoms Shixi wafer. In the typical embodiment shown in Figure 2, the state or vaporous feed material containing helium, nitrogen and hydrogen is supplied to the vacuum capacity = 10 by the distribution systems n and 12. The plasma source 5 of high frequency electromagnetic energy (preferably pulsed microwave energy) will ignite the plasma discharge 6 under appropriate vacuum conditions. The tantalum nitride film 2 will be placed on the handling and heating platform 8 based on the high temperature. The semi-finished Dream wafer 3 is formed on the photovoltaic cell 7, while hydrogen atoms diffuse into the wafer into the wafer in 200910426 to passivate the dangling bond. The advantage is that the feed material containing ruthenium is not decane, but is, for example, hexamethyl An organic ruthenium compound of diazane. [Embodiment] The production of a photovoltaic cell 7 based on a semi-finished germanium wafer (shown in FIG. 2 but with a thermal tantalum nitride layer 2 and a front contact grid 1) is loaded. The vacuum vessel is placed inside the crucible and placed on the handling and heater platform 8. The residual gas pressure within the vessel must be low enough to avoid primarily oxygen contamination of the deposited film. Frequent exhaust of the container should therefore be avoided between operating cycles. + The cycle is initiated by a gas distribution system 丨丨 and 12 to feed the feed gas or helium into the vessel. The enthalpy-containing feed distribution system is preferably located between the photovoltaic cell 7 and the electric paddle source 5, and all other gaseous feed materials are borrowed from another feed distribution system on the opposite side of the propeller source 5. In. Of course, all necessary feed materials can also be fed by a single distribution system 'but the post-plasma source, 5 will experience the usual undesired self-coating of all feed gases for non-magnetized CVD. The proper pressure (between 0.05 and lhPaP gas, Wang 1 iih) has stabilized, and the handling and heater platform 8 has heated the photovoltaic cell to the desired temperature (usually between the xiaojia c) After the method and the wafer material, the plasma discharge 6 at the electropolymer source 5 will be ignited by the power or electromagnetic energy supplied by the appropriate energy source. During the formation of the film, it is also possible to continuously move the photovoltaic layer 7 into the film formation region and to remove it again. / U selects a very high electromagnetic frequency of, for example, 245 〇 〜 ~ because of the high plasma density that can cause high film deposition rates is desirable. Gaseous or vaporous non-materials in the waste distribution system & 12 200910426 will pass through the plasma zone 6 during the movement to the vacuum pumping port 9,9. In the electro-chemical region, the feed molecules will be dissociated, free-fielded, intensified, or ionized depending on the type of interaction with the plasma particles or plasma radiation. The specific portion of the feed molecules will be energized when moving toward the photovoltaic and vacuum pump ports 9, 9; the latter position can be as shown in Figure 2, but can also be located behind the handling and heating platform 8. The ruthenium-containing feed material fed by the distribution system 11 will also move toward the vacuum 9 9 . Since the 7 molecules do not pass through the plasma region, they are formed by the interaction of the radiation and the nitrogen-containing feed molecules excited by the energy to excite and resolve the various energy excitations of the wafer surface. Nitriding the (tetra) film' and supplying hydrogen atoms to the dream wafer to purify the suspended bonds. However, the precise location of the feed to the rhodium-containing feed material may depend on the general method strip #, the desired deposition rate and, for example, charcoal. The allowable amount of other atoms in the antireflective film. It may therefore be necessary to expose the material containing the stone (4) directly to the plasma. Since the invention of this patent application is based on the replacement of decane gas by an organic compound such as hexamethyldiazepine (chemical formula (CH3)3-Si-NH-Si-(CH3)3), individual Effective cleavage of the molecule and simultaneous inhibition of the inclusion of carbon atoms into the antireflective film will be important. The degree of molecular cracking caused by plasma discharge depends mainly on the temperature of the electropolymerized electrons, the density of the electrical destruction, and the intensity of the vacuum ultraviolet (four) from the plasma. The cracking is preferably such that the carbon still maintains or forms a volatile hydrocarbon compound which can ultimately be withdrawn from the process zone by means of a vacuum pump port 7 3 . The ratio of the flow rate between the helium-containing gas feed material and the remaining feed material is usually set to 200910426 so that a stoichiometric gasification fossil (chemical formula w#4) can be formed. However, different types of photovoltaic cells based on Shi Xi will need to adjust the composition of gasification. The goal of all adjustments is to maximize the efficiency of photovoltaic cells. When the hydrogen content of the feed material containing the diarrhea and nitrogen is insufficient to sufficiently purify the stellate crystal, molecular hydrogen can be added to the electricity storage method. In order to achieve high deposition rates, appropriate molecular cracking of the feed material, and increased spatial uniformity of the deposition process, the plasma source 5 can be supplied with microwave energy (preferably 2450 MHz) and can be operated in a pulsed mode. Preferably, the peak height of the rectangular pulse is preferably several times higher (e.g., five times) than the equivalent continuous wave level which results in an acceptable deposited film result. The ratio of the on pulse to the off pulse should be set to the reciprocal of the peak power ratio. The plasma source 5 and feed material distribution systems η, 12 as shown in Figure 2 can be mounted above or below the photovoltaic cell 7. The handling and heating platform 8 needs to be adjusted accordingly. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a cross-sectional view showing a photovoltaic cell based on a germanium wafer. It basically consists of a doped germanium wafer 3 as a light absorber, a rear electrode 4, a front electrode tear 1 and an antireflection film 2. Fig. 2 is a view showing an example of a reactor for depositing an antireflection film on a photovoltaic cell based on a ray wafer by plasma enhanced chemical vapor deposition. The reactor consists of a vacuum vessel 10, a photovoltaic cell 7 placed on the handling and heating platform 8, a plasma source 5 with plasma 6, pumping ports 9, 9 and feed material distribution systems 11 and 12. [Main component symbol description] 200910426 1 Front electrode 2 Tantalum nitride film (anti-reflection layer) 3 Mixed wafer 4 Rear electrode 5 Plasma source 6 Plasma discharge 7 Photovoltaic battery 8 Handling and heating platform 9 Vacuum pump port 9, vacuum pump port 10 vacuum vessel 11 feed material distribution system 12 feed material distribution system 12

Claims (1)

200910426 十、申請專利範面： 種在化予氣相沉積法期間、於基於矽晶圓的光伏 電池上產生氮化矽抗反射薄膜且同時將氫原子擴散至矽晶 圓内的方法，該方法係含有： 適用於化學氣相沈積法的真空容器，以在適當的高 下包含基於矽晶圓的光伏電池， -用於形成至少一個電喈诒雪 源 質 电浆放電的至少一個電磁能量來 以攸氣體進料物質中產决白士 I儿上 貝甲屋生自由基化或能量激發的物 、3有石夕氫、氮與碳的第一氣態或汽態進料物質， 只含有氮與氫的第二氣態或汽態進料物質 只含有氫的第三氣態或汽態進料物質。 2. 如申請專利範圍第1 —β k 項之方法’其中該第一氣態或 八悲進料物質是不含氧之有機矽化合物。 3. 如申請專利範圍第2 , 項之方法，其中該第一氣態或 凡態進料物質是具有化學式 马（CH3)3-Si-：KH-Si-(CH3)3 的六 曱基二矽氮烷。 4. 如申請專利範圍第1至3 卜 王。項1f任一項之方法，其中 該第二氣態或汽態進料物質传 , 物負係具有化學式為NH3的氨氣。 5. 如申請專利範圍第丨 ^ ^ ^ 孭肀任一項之方法，其中 該第二氣態或汽態進料物質是分子氫。 6. 如申請專利範圍第i 土甲任一項之方法，其中 該能量來源是微波能量來源。 ” 7·如申請專利範圍第6 項之方法，其中該微波能量來 13 200910426 源係以9丨5 MHz或2450 MHz操作。 8.如申請專利範圍第丨至3 該能量來源可以製造脈衝輪出 ^方法’其中 連續波能量程产之方L 、中與相關的最大可接受 、 又 法相比，在脈衝期間的尖峰能量程度 係遠遠較高，且開脈衝的持續時 衝時間。 ㈣孖躓時間係通遠短於個別的關脈 9.如申請專利範圍第…項中任一項之方法，立中 操：氣體壓力係介於0.05…與i hpa的範圍間，且：真 空各器内的殘留氣體壓力係低於〇 〇〇〇1 hpa。 10_如申請專利範圍第9項之方法，其中該電漿並未 與基於矽晶圓之光伏電池表面有肉眼可見之接觸。 11_如申請專利範圍第1至3項中任一項之方法，其 中該基於矽晶圓之光伏電池係在薄膜產生方法過程中於真 空容器内移動。 、 十一、圈式： 如次頁。 14200910426 X. Patent application: A method for producing a tantalum nitride antireflection film on a germanium wafer-based photovoltaic cell while diffusing hydrogen atoms into the germanium wafer during the vapor deposition process. Containing: a vacuum vessel suitable for chemical vapor deposition to contain a wafer based photovoltaic cell at an appropriate height, - for forming at least one electromagnetic energy of at least one electric snow source plasma discharge In the helium gas feed material, the first gaseous or vaporous feed material containing the free radical or energy excitation of the shellfish, the third gaseous or vaporous feed material with the hydrogen, nitrogen and carbon, contains only nitrogen and The second gaseous or vaporous feed material of hydrogen contains only a third gaseous or vaporous feed material of hydrogen. 2. The method of claim 1 - β k wherein the first gaseous or sacred feed material is an oxygen-free organic cerium compound. 3. The method of claim 2, wherein the first gaseous or gaseous feed material is a hexamethylenedifluoride having the chemical formula (CH3)3-Si-:KH-Si-(CH3)3 Azane. 4. If you apply for patents 1 to 3, King. The method of any of item 1f, wherein the second gaseous or vaporous feed material is passed through an ammonia gas having the chemical formula NH3. 5. The method of claim 1, wherein the second gaseous or vaporous feed material is molecular hydrogen. 6. The method of claim 1, wherein the source of energy is a source of microwave energy. 7. The method of claim 6, wherein the microwave energy is 13 200910426. The source is operated at 9丨5 MHz or 2450 MHz. 8. If the application scope is 丨 to 3, the energy source can be used to make a pulse round. ^Method 'Where the continuous wave energy process produces the L, the medium and the correlation maximum acceptable, and the method, the peak energy level during the pulse is much higher, and the continuous pulse duration of the pulse. (4) The time system is much shorter than the individual pulse. 9. For the method of any one of the patent application scopes, the middle pressure operation: the gas pressure system is between 0.05... and i hpa, and: in the vacuum The residual gas pressure is less than 〇〇〇〇1 hpa. 10_ The method of claim 9, wherein the plasma does not have visible contact with the surface of the photovoltaic cell based on the ruthenium wafer. The method of any one of claims 1 to 3, wherein the wafer-based photovoltaic cell moves within the vacuum vessel during the film production process., eleven, and laps: as in the next page.
TW096131319A 2006-07-27 2007-08-23 Silane free, plasma enhanced chemical vapour deposition of silicon nitride as an antireflective film and for hydrogen passivation of silicon wafer based photovoltaic cells TW200910426A (en)

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