201034235 六、發明說明： 【發明所屬之技術領域】 本發明係關於一種製程方法，特別關於一種半導體元 件的製程方法。 【先前技術】 由於目前全球的石油化燃料逐漸枯竭，因此人們積極 尋找及開發替代的能源，如太陽能發電、風力發電及水力 發電…等，而其中係以太陽能的利用為最主要的技術發展 方向，其因在於太陽光可照射在全球各個地區，且太陽能 在進行轉換的過程不會對環境造成汙染，舉例來說，在太 陽光能轉換為電能的過程中，無須藉由消耗其他能源而導 致溫室效應的問題。然而，太陽能轉換為電能的轉換效率 卻容易受限於整個太陽能電池系統的機構設計。 太陽能電池最基本的結構可分為基板、p-n二極體、 抗反射層及金屬電極四個主要部份。基板為太陽能電池的 主體；p-n二極體是光伏特效應的來源；抗反射層乃用於 減少入射光的反射以增強電流；金屬電極則是連接元件和 外部負載。其各個構件都具有繁複之製程，其製程方法之 成效都可能影響太陽能光電轉換之效率，因此，業界注入 龐大的資金以及人力去研究太陽能電池之製程方法，以獲 得較高之效能。 現今晶矽太陽能電池的效率理論值最高達27%，研發 階段約為24%，到產品商品化約只有16〜18%。因此，如 201034235 何提供半導體元件的製私方法，提高太陽能電池之光電轉 換效率，已成為重要課題之一。 【發明内容】 有鑑於上述課題，本發明之目的為提供一種半導體元 件的製程方法於半導體元件製程之後，提供一可改變氣 體或混合氣艨之環境，致使氣體原子或離子可與半導體元 件之表面和内部起反應，以提高半導體元件之光電轉換效 φ 率。 為達上述之目的，本發明提供一種半導體元件的製程 - 方法，其係包含下列步驟：提供一半導體基板；清洗半導芝 : 體基板；將爭導體基板之第一表面進行結構化處理；將半： 導體基板之第一表面進行擴散；塗佈一抗反射層於半導體：,. 基板之第一表面上；形成至少一電極層於半導體基板之第營 一表面上並構成一半導體元件；以及提供一可改變之氣體 環境，致使氟艘原子或離子可與半導體元件之表面和内部 ® 起反應，以提升光電轉換效率。 承上所述，本發明之半導體元件的製程方法係可應用 於太陽能電池之半導體元件，於一可改變氣體之環境下， 該氣體可包含各式各樣氣體分子，如氮氣、氫氣、氧氣、 氨氣、石夕甲烧（SiH4 )、曱烷（CH4 )、惰性氣體或其組合 等，而改變氣體環境之因素可包含熱能、電磁波、電場和 磁場等，上列因素可以是單一或數種同時改變，如此可導 致該氣體原子或離子與半導體元件反應後可有下列功 201034235 能：可使已氧化之金屬還原，致使半 導體元件之電極電阻 p奢低’同時該氣體原子可與半導體元件内部之缺陷結合， 致使減y復合中心’此外亦能在半導體元件表面形成凹凸 不平形狀’而產生將八射光補捉之效果，因此*達到較高 的光電轉換效率。 【實施方式】 以下將參照相關圖式，說明依本發明較佳實施例之一 種半導體it件的製程方法，其中相同的元件將以相同的參 照符號加以說明。 睛參照® 1所*，其為本發明之半導體元件的製程方 法之一流程步驟圖。其製程方法包含步驟81至步驟Μ。 步驟S1提供-半導體基板。其半導體基板係為一石夕 基板’其石夕基板又分為單晶梦基板、多晶硬基板、非晶石夕 基板或微晶矽基板。另外，本實施例中係以多晶矽基板舉 例說明，然非用以限制本發明。 步驟S2清洗半導體基板。半導體基板之清洗製程係 以超純水與化學溶劑，去除晶圓表面各種微小顆粒（舉例 但不限於奈米微粒）’並反覆進行清洗製程，直到半導體 基板表面已完全清潔。 本實施例之半導體基板具有一第一表面。步驟S3將 半導體基板之第一表面進行結構化處理。其係以HC1、KOH 等溶液做非等向性钱刻（anisotropic etching )，而粗化半導 體基板之第一表面，去哮表面的金屬雜質及有機物等之附 201034235 著，同時也對表面產 而提高太陽能電池光轉構’降低光線的反射，進 步驟S4將半導體 基板為N型半導體心/之第—表面進行擴散。半導體 為N型半導體基板型半導體基板。當半導體基板 體基板上；當半導軌：料導體㈣擴散至N型半導 導體材料_至P型；，P型半導體基板’則將 N型半 板係以P型半導體基體基板上。本實施例中半導體基 電洞的再結合形成詩例。在P_N接面附近’因電子-層中也因分別帶有負财空乏區，而P型及㈣半導體 當太陽光照射到這以正電荷’因此形成—個内建電場。 收太陽光而產生電子、構_ ρ^σΝ^半導體層因吸 電場，會使電子和電；電洞對。由於空乏區所提供的内建 進行產生錢流。77職Ν型區域及？魏域移動， 步驟S5塗佈—抗反射層於半導體基板之第」表面 上。由於空氣與矽的折射係數差異甚大，光線通過空氣與 矽的介面時會有明顯光線反射情形，因此以氮化矽（SiNx) 材質之抗反射層塗佈於半導體基板，以減少入射光的反 射，而且氮化矽對矽晶太陽能電池表面還有純化 (passivation)之作用，進而提升整體之效能。另外，也 可以成長其他對矽晶太陽能電池表面具有抗反射及鈍化 效果之材質。 步驟S6形成至少一電極層於半導體基板之第一表面 上並構成一半導體元件。於第一表面形成之電極層具有複 201034235 數匯流電極（bus bar electrode )及複數指狀電極（finger electrode )。該等指狀電極及該等匯流電極設置於第一表面 上，而該等指狀電極與至少一匯流電極電性連接，當半導 體基板將吸收到的光線轉變為電子時，其該等指狀電極用 於將半導體基板所產生之電子匯集至相電性連接之匯流 電極。最後，藉由匯流電極與外部負載的連結，以將經過 光、電轉換反應所產生的電子傳遞至外界。本實例中之半 導體元件係可為一光電轉換模組。 另外，本實施例之半導體基板更包含一第二表面，其 與第一表面相對設置，分別於半導體基板之正反面設置， 本實施例係以第一表面為正面，而第二表面為反面為例， 本實施例更包含於第二表面形成一電極層，使增加多數載 子的吸收，並反彈少數載子。其中，第一表面之電極層為 負極，第二表面之電極層為正極。 步驟S7提供一可改變氣體之環境，並同時提供可改 變氣體環境之因素，該因素係包含熱能、電磁波、電場、 磁場、或是上述因素之各種組合，致使氣體原子或離子可 與半導體元件之表面和内部起反應，以提升光電轉換效 率，其係為氣體原子或離子與半導體元件之反應製程。 本實施例係將氣體提供至一電漿產生器，以產生具有 該氣體之電漿，並提供熱能至半導體元件，致使電漿與半 導體元件内部反應，以提升光電轉換效率。 本實施例中其提供能量予半導體元件之反應溫度為 25〜800°C，而熱能的來源可為電阻源、熱風、遠紅外線烘 201034235 烤機（IR lamp)、微波或雷射等。反應時間大約幾分鐘或 者更久之時間，其依據所設定溫度及其升溫/降溫速率而 定。其中，氣體環境之氣體可為單一氣體或混合氣體。另 外，氣體環境可包含氫氣、氧氣、氮氣、氨氣、惰性氣體、 矽曱烷（SiH4)、曱烷（CH4)或其組合等，其中，惰性氣 體可為氦、氖、氬、氪、氙、氡，而氫氣的濃度係介於2% 至95%之間。 由於反應溫度範圍内，半導體元件内之缺陷易與反應 參氣體原子結合，以降低復合中心（recombination center)， 進而提升光電轉換效率。因光電轉換效能（gain)t的定義 為每吸收一個光子能在電極處得到幾對電子電洞對，若於 能階中含有復合中心，則復合中心會再結合（recombine ) 照光所形成的部份載子（電子及電洞），因此減少到達輸 出電極的載子數量，造成光電轉換效應下降。 另外，混合氣體之原子可使得半導體元件之金屬氧化 物還原，提升導電性，進而提升先電轉換模組之整體效 馨 • 能。同時該混合氣體可以在半導體元件表面形成凹凸不平 結構，捕捉入射光，增加光電轉換效率。另外，也可對矽 晶太陽能電池產生鈍化之效果，減少復合中心，提升光電 流及操作電壓。經實驗驗證：效能可以增加0.1%〜0.5%。 最後，於提供能量予半導體元件之後，以冷卻水、壓 縮空氣、液態氮或其他冷卻裝置冷卻半導體元件，直到半 導體元件降至室溫之溫度。 綜上所述，本發明之半導體元件的製程方法係可應用 201034235 於太陽能電池之半導體元件，於一可改變氣體之環境下， 使半導體元件之缺陷與氣體之原子或離子相結合，此能降 低復合中心，其中、，氣體可包含各式各樣氣體分子，如氮 氣、氫氣、氧氣、氨氣、矽甲烷（SiH4 )、曱烷（CH4)、 惰性氣體或其組合等，而改變氣體環境之因素可包含熱 能、電磁波、電場和磁場等，上列因素可以是單一或數種 同時改變；同時，本發明之製造方法也可還原半導體元件 之金屬氧化物及其他化合物，致使半導體元件之電極電阻 降低，進而提升半導體元件之導電性，此外該混合氣體亦 可在半導體元件產生凹凸不平結構，捕捉入射光，因此達 到較高的光電轉換效率。 以上所述僅為舉例性，而非為限制性者。任何未脫離 本發明之精神與範疇，而對其進行之等效修改或變更，均 應包含於後附之申請專利範圍中。 【圖式簡單說明】 圖1為本發明之半導體元件的製程方法之一流程步驟 圖。 【主要元件符號說明】 S1〜S7 :步驟 10201034235 VI. Description of the Invention: TECHNICAL FIELD OF THE INVENTION The present invention relates to a process method, and more particularly to a process method for a semiconductor device. [Prior Art] As the world's petrochemical fuels are gradually depleted, people are actively seeking and developing alternative energy sources such as solar power, wind power and hydropower... among them, the use of solar energy is the most important technology development direction. The reason is that sunlight can be irradiated in various parts of the world, and the process of conversion of solar energy does not pollute the environment. For example, in the process of converting solar energy into electric energy, it is not necessary to consume other energy. The problem of the greenhouse effect. However, the conversion efficiency of solar energy into electrical energy is easily limited by the mechanical design of the entire solar cell system. The most basic structure of a solar cell can be divided into four main parts: a substrate, a p-n diode, an anti-reflection layer, and a metal electrode. The substrate is the body of the solar cell; the p-n diode is the source of the photovoltaic effect; the anti-reflective layer is used to reduce the reflection of incident light to enhance the current; the metal electrode is the connecting element and the external load. Each of its components has a complicated process, and the effectiveness of its process methods may affect the efficiency of solar photovoltaic conversion. Therefore, the industry has injected huge capital and manpower to study the solar cell process methods to achieve higher performance. Today, the theoretical value of solar cell solar cells is up to 27%, the research and development stage is about 24%, and the commercialization of products is only about 16~18%. Therefore, as for the method of manufacturing semiconductor components in 201034235, it has become one of the important topics to improve the photoelectric conversion efficiency of solar cells. SUMMARY OF THE INVENTION In view of the above problems, an object of the present invention is to provide a method for fabricating a semiconductor device, which provides an environment for changing a gas or a mixed gas after the semiconductor device is processed, so that gas atoms or ions can be combined with the surface of the semiconductor device. Reacts with the inside to improve the photoelectric conversion efficiency of the semiconductor element. To achieve the above object, the present invention provides a process for a semiconductor device, comprising the steps of: providing a semiconductor substrate; cleaning a semiconductor substrate; and structuring the first surface of the conductor substrate; a first surface of the conductor substrate is diffused; an anti-reflective layer is coated on the first surface of the semiconductor substrate; and at least one electrode layer is formed on the first surface of the semiconductor substrate to form a semiconductor component; Providing a modifiable gas environment that causes fluorine atoms or ions to react with the surface and interior of the semiconductor component to improve photoelectric conversion efficiency. As described above, the manufacturing method of the semiconductor device of the present invention can be applied to a semiconductor device of a solar cell, and the gas can contain various gas molecules such as nitrogen, hydrogen, oxygen, and the like in a gas-changing environment. Ammonia gas, Shixijia (SiH4), decane (CH4), inert gas or a combination thereof, and the factors that change the gas environment may include thermal energy, electromagnetic waves, electric fields and magnetic fields, etc. The above factors may be single or several Simultaneously changing, this can cause the gas atom or ion to react with the semiconductor element and can have the following work 201034235: the oxidized metal can be reduced, so that the electrode resistance of the semiconductor element is extravagantly low, and the gas atom can be combined with the inside of the semiconductor element. The combination of the defects causes the y-recombination center 'to also form an uneven shape on the surface of the semiconductor element' to produce an effect of capturing the eight-light, and thus* achieves a high photoelectric conversion efficiency. [Embodiment] Hereinafter, a method of manufacturing a semiconductor device according to a preferred embodiment of the present invention will be described with reference to the accompanying drawings, wherein like elements will be described with the same reference numerals. The eye refers to ® 1*, which is a flow chart of one of the manufacturing methods of the semiconductor device of the present invention. The process method includes steps 81 through Μ. Step S1 provides a semiconductor substrate. The semiconductor substrate is a stone substrate. The stone substrate is further divided into a single crystal dream substrate, a polycrystalline hard substrate, an amorphous slab substrate or a microcrystalline substrate. Further, in the present embodiment, the polycrystalline germanium substrate is exemplified, but it is not intended to limit the present invention. Step S2 cleans the semiconductor substrate. The cleaning process of the semiconductor substrate is to remove ultra-pure water and chemical solvents to remove various fine particles on the surface of the wafer (for example, but not limited to nano particles) and to carry out the cleaning process until the surface of the semiconductor substrate is completely clean. The semiconductor substrate of this embodiment has a first surface. Step S3 structuring the first surface of the semiconductor substrate. It is anisotropic etching using a solution such as HC1, KOH, etc., and roughens the first surface of the semiconductor substrate, and the metal impurities and organic substances on the surface of the rotting surface are attached to 201034235, and also on the surface. Increasing the solar cell light conversion 'reduces the reflection of light, and proceeds to step S4 to diffuse the semiconductor substrate to the surface of the N-type semiconductor core. The semiconductor is an N-type semiconductor substrate type semiconductor substrate. On the semiconductor substrate substrate; when the semi-rail: material conductor (4) is diffused to the N-type semiconductor material_to the P-type; the P-type semiconductor substrate' is the N-type half-plate on the P-type semiconductor substrate. The recombination of the semiconductor-based holes in this embodiment forms a poem. In the vicinity of the P_N junction, the P-type and (4) semiconductors have a built-in electric field when they are irradiated with positive energy by the negative electron-causing area, respectively. Receiving sunlight and generating electrons, the structure _ ρ ^ σ Ν ^ semiconductor layer due to the absorption of electric field, will make electrons and electricity; The money flow is generated by the built-in provided by the depletion zone. 77 job area and? The Wei domain moves, and the step S5 coats the antireflection layer on the first surface of the semiconductor substrate. Since the refractive index difference between air and helium is very large, when light passes through the interface between air and helium, there is obvious light reflection. Therefore, an anti-reflective layer made of tantalum nitride (SiNx) is applied to the semiconductor substrate to reduce the reflection of incident light. And the tantalum nitride also has a passivation effect on the surface of the twinned solar cell, thereby improving the overall performance. In addition, other materials that have anti-reflection and passivation effects on the surface of the twin solar cell can be grown. Step S6 forms at least one electrode layer on the first surface of the semiconductor substrate and constitutes a semiconductor element. The electrode layer formed on the first surface has a plurality of 201034235 bus bar electrodes and a plurality of finger electrodes. The finger electrodes and the bus electrodes are disposed on the first surface, and the finger electrodes are electrically connected to the at least one bus electrode. When the semiconductor substrate converts the absorbed light into electrons, the fingers are The electrodes are used to collect electrons generated by the semiconductor substrate into the electrically connected junction bus electrodes. Finally, the electrons generated by the photo-electrical conversion reaction are transmitted to the outside by the connection of the bus electrode to the external load. The semiconductor component in this example can be a photoelectric conversion module. In addition, the semiconductor substrate of the embodiment further includes a second surface disposed opposite to the first surface and disposed on the front and back surfaces of the semiconductor substrate. In this embodiment, the first surface is a front surface, and the second surface is a reverse surface. For example, the embodiment further includes forming an electrode layer on the second surface to increase the absorption of the majority carrier and rebound a minority carrier. The electrode layer on the first surface is a negative electrode, and the electrode layer on the second surface is a positive electrode. Step S7 provides an environment in which the gas can be changed, and at the same time provides a factor that can change the gas environment, which includes thermal energy, electromagnetic waves, electric fields, magnetic fields, or various combinations of the above factors, so that the gas atoms or ions can be combined with the semiconductor elements. The surface reacts internally to enhance the photoelectric conversion efficiency, which is a reaction process of gas atoms or ions with semiconductor components. This embodiment supplies a gas to a plasma generator to produce a plasma having the gas and provides thermal energy to the semiconductor element, causing the plasma to react internally with the semiconductor element to improve photoelectric conversion efficiency. In this embodiment, the reaction temperature for supplying energy to the semiconductor element is 25 to 800 ° C, and the source of thermal energy may be a resistance source, a hot air, a far infrared ray drying, an IR lamp, a microwave or a laser. The reaction time is about a few minutes or longer, depending on the set temperature and its rate of temperature rise/fall. The gas in the gaseous environment may be a single gas or a mixed gas. In addition, the gaseous environment may include hydrogen, oxygen, nitrogen, ammonia, an inert gas, decane (SiH4), decane (CH4) or a combination thereof, wherein the inert gas may be ruthenium, osmium, argon, krypton or xenon. , 氡, and the concentration of hydrogen is between 2% and 95%. Due to the reaction temperature range, defects in the semiconductor element are easily combined with the reaction gas atoms to lower the recombination center, thereby improving the photoelectric conversion efficiency. The photoelectric conversion efficiency (gain) is defined as the number of pairs of electron holes that can be obtained at the electrode for each photon absorbed. If the composite center is included in the energy level, the composite center will recombine the portion formed by the illumination. The carrier (electrons and holes), thus reducing the number of carriers reaching the output electrode, resulting in a decrease in the photoelectric conversion effect. In addition, the atoms of the mixed gas can reduce the metal oxide of the semiconductor element, improve the conductivity, and further improve the overall efficiency of the first power conversion module. At the same time, the mixed gas can form an uneven structure on the surface of the semiconductor element, capturing incident light, and increasing photoelectric conversion efficiency. In addition, the effect of passivation on the twin solar cells can be reduced, the recombination center can be reduced, and the photocurrent and operating voltage can be increased. It has been verified by experiments that the efficiency can be increased by 0.1%~0.5%. Finally, after supplying energy to the semiconductor component, the semiconductor component is cooled with cooling water, compressed air, liquid nitrogen or other cooling means until the semiconductor component drops to room temperature. In summary, the manufacturing method of the semiconductor device of the present invention can be applied to the semiconductor component of the solar cell of 201034235, and the defect of the semiconductor component is combined with the atom or ion of the gas in a gas-changing environment, which can reduce a composite center, wherein the gas may contain various gas molecules such as nitrogen, hydrogen, oxygen, ammonia, helium methane (SiH4), decane (CH4), an inert gas or a combination thereof, etc., and change the gaseous environment. The factors may include thermal energy, electromagnetic waves, electric fields, magnetic fields, etc., and the above factors may be single or several simultaneous changes; meanwhile, the manufacturing method of the present invention may also reduce metal oxides and other compounds of the semiconductor elements, resulting in electrode resistance of the semiconductor elements. The electric conductivity of the semiconductor element is lowered, and the mixed gas can also generate an uneven structure on the semiconductor element to capture incident light, thereby achieving high photoelectric conversion efficiency. The above is intended to be illustrative only and not limiting. Any equivalent modifications or alterations to the spirit and scope of the present invention are intended to be included in the scope of the appended claims. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a flow chart showing a process of a semiconductor device of the present invention. [Main component symbol description] S1~S7: Step 10