200917348 九、發明說明： 【發明所屬之技術領域3 發明領域 本發明概有關一種用以清潔表面的裝置和方法，且尤 5 係有關由半導體晶圓表面來除去有機膜、微粒物及其它污 染物，而具有減少的殘留雜質和污染物者。 I：先前技術3 發明背景 由於奈米級的構形已在半導體、MEMS、儲存體、先 10 進的封裝及其它技術領域中變成標準規格，故新的技術乃 被研發來解決由重要表面除去次微米污染物的問題。電水 動力學(EHD)可造成速度受控的奈米細滴，其會呈現特別適 合於該等清潔挑戰的性質。電水動力的霧化包括使用一導 電流體，其會被打散並配佈於一帶電的奈米細滴束中。為 15 造成一EHD束，一靜電應力會被施加於該導電流體之液柱 曲面，該應力會超過保持該曲面完整的表面張力。 在一典型的EHD系統中，一小流體貯槽會容裝一要被 喷灑的導電性處理化學流體，且一在該貯槽中的電接點會 施一電位於該流體。一氣壓控制器會施一受控的壓力於該 20 貯槽内的流體，而造成一流體流由該貯槽穿過一毛細管並 進入一在該毛細管的噴灑端（或實際的喷嘴）之靜電場。EHD 奈米細滴的產生係藉貯槽的充電程度和在該喷嘴處的電場 操縱來被電控制。該等奈米細滴的速度和大小可被改變， 而造成一寬廣範圍的製程設定以使該等奈米細滴匹配於該 200917348 等污染物和基材。奈米細滴係可針對動量移轉至微粒的理 想耦合而來被造成。EHD裝置和方法曾被揭於美國專利No. 6,033,484中，名稱為“使用強力的聚團束來清潔被污染表面 的裝置（Mahoney)，其完整揭露併此附送；及美國專利No. 5 5,796,111中，名稱為“使用強力的聚團束來清潔被污染表面 的方法和裝置”(Mahoney)，其全部内容併此附送。習知電 喷灑液體之例包括水、醇類（甲醇、2-丙醇(IPA)、乙醇）、 甘油、經胺、η-曱基B比1^_(NMP)，及硫酸。 雖EHD噴灑液體溶液能有效地清潔表面和基材，但在 10 該喷嘴處於露化之前既存於該溶液中的前身質固體或氣體 雜質會在該等細滴形成之後被滯陷並分佈其中。當撞擊一 基材或表面時，因破碎和蒸發而崩散的細滴會釋放所含帶 的雜質，致造成一不良的污染源。 又，在電極/電解液化學物中的某些化合物亦會導致非 15 揮發性分子種物的形成，其會向下游流至該喷嘴處而被含 納在形成於霧化區中的細滴内。 另一污染源係有關由該等細滴與“背景”氣體和基材原 料交互作用所產生之製程致生的污染物。若該基材原料係 為一矽晶圓，則“瑕疵”測繪設備例如一KLA-Tensor SP2會 20 顯示該EHD束會造成可歸因於上述污染源的“光點瑕 疵，，(LPD)。 因此有須提供一種改良之用以清潔表面的EHD喷灑溶 液裝置和方法，其能最少化殘留的表面雜質，包括在霧化 前由該喷灑溶液中的前身質固體或氣體雜質所形成者，及 200917348 因射束細滴等與背景氣體和基材原料交互作用所產生者。 t發明内容3 發明概要 本發明係有關一種以電喷灑的微滴束來除去表面污染 5 物的系統和方法，而具有較少之可歸因於該等微滴本身的 殘留污染物者。該系統和方法可被用來清潔表面，或甚至 結構化、蝕刻或塗層該等表面。在一實施例中，該系統包 含一源頭構製成可對該表面產生一聚團射束，該源頭具有 " 一開口，一饋供系統構製成可饋供一液體至該開口，及一 10 處理系統構製成可由該液體除去雜質。該源頭包含一裝置 構製成可產生一電場來施加比在該開口處的液體之表面張 力更高的靜電力。 在本發明之一更詳細的實施例中，該處理系統包含一 除氣器用以由該液體排除氣體。一過濾器用以由該液體排 15 除微粒，及一泵用以使該液體循環於該饋供系統和處理系 統之間。又，該饋供系統包含一貯槽其係由低粒子脫落和 L 化學阻抗性的材料所構成，且該泵會以一超過對該開口流 率的高容積流率來循環該液體。 在另一更詳細的實施例中，該系統包含一電極其會充 20 電該液體。依據本發明之一特徵，該電極可包含單原子的 金屬元素，二元的金屬合金，三元的金屬合金，四元的金 屬合金，及/或玻璃狀碳，且所選之介於該電極與該液體之 間的化學物會導致不同種物的形成，其能被該處理系統以 減少可歸因於該電喷麗液體之殘留表面污染物的方式來有 7 200917348 效地處理。 本發明之一方法包括：提供一源頭構製成可由一開口 產生一聚團射束，饋供一液體至該開孔，及由該液體除去 雜質，其中該源頭會產生一電場來施加比該液體在該開口 5 處之表面張力更高的靜電力。 在本發明之一詳細實施例中，由該液體除去雜質包含 將該液體除氣。過濾該液體，及循環該液體通過一除氣器 與一過濾器。且，本發明包含加熱構件，包含一封殼其中 該聚團射束會被產生，提供内部的靜電板靠近該射束來吸 10 引該射束中的離子種物，及/或靠近該射束促成該射束内之 氣體種物的冷凝。 在本發明之一更詳細的實施例中，該封殼能被加熱到 至少150°c經至少30分鐘，且面板可被低溫地冷却來促進冷 凝。又，該液體的化學物及一充電電極可被選成能使該電 15 極處的氧化反應導致氣體產物或不可溶解層的形成，其會 留存在電極上而不會進入該溶劑。施於該電極的電壓之極 性亦會影響被形成的種物。 本發明之這些及其它的特徵和優點等將可配合所附圖 式參閱以下的詳細說明來考量而更佳地瞭解。應請瞭解有 20 些選擇的結構和特徵並未被示於某些圖式中，俾能提供其 餘的結構和特徵之較佳的視圖。 圖式簡單說明 第1圖示出在一 EHD系統之一貯槽内之一溶液與一電 極之間的電化學反應。 200917348 第2圖不出由 ρττΤΛ 4+ ik 田—EHD射束細滴形成一奈米聚團。 第3圖為〜矛立闽一山 思圖不出—依據本發明的系統之實施例。 弟3a圖為〜千立同—山 不思圖不出〜依據本發明的糸統之變化實 施例。 5【實施冷式】 較佳實施例之詳細說明 本發明察覺在一 EHD噴觀溶液霧化前之一污染源乃包 括含帶有分開的污染分子之細滴，它們係經由多種來源被 引入该EHD溶液中，包括污染的初始溶液及由 —EHD 裝 10置中之/亏染構件和管道脫落的微粒等。 本發明亦得知在霧化前之另一污染源乃包括要被喷麗 的〉谷液和會施加電壓並充電讀溶液的電極之間的化學交互 作用。如第1圖中所示，一摻有一導電添加劑AC的溶液1〇 係被谷農在一電解槽或絕緣的貯槽12中。相鄰的成對分子 15 AC會存在於該溶液中作為未分解的電解質或溶質分子，其 會形成陰陽離子對。相鄰的成對分子會分解成溶液陰離 子A和溶液陰離子〇其皆取決於該添加劑ac的特定化學物 及一浸入之充電電極14的極性，而能與該電極的材料]Vi交 互作用來形成新的分子MA或MC。 20 若該等新分子係為一揮發性的氣體種物，則該等分子 會無害地升高至該溶液上方而能被泵出，但若該電極/溶液 的化學物會產生一非揮發性種物的新分子，則它們會被該 溶液傳送至該喷嘴處而在該電喷灑的細滴中提供一不良的 污染源。這些非揮發性污染物會沈積在基材上，其係截阻 200917348 於該霧化區的射束下游。例如，若該電極材料Μ是金，該 導電添加劑為氫氯酸(HC1)，且該金電極係連接於一正電壓 源，則AuCl分子種物會由該電極與該導電添加劑之間的電 解反應產生，其在該等細滴中的聚結會生成AuCl奈米團， 5 它們在噴飛的射束細滴蒸發之後將會自由游移。 其它的電極/電解液化學物會導致非揮發性之不可溶 種物的形成，其會形成不可溶化層留存在該電極上而不進 入該溶液中。例如，若該電極是銀，且該導電添加劑為HC1， 則會產生分子種物AgCl，其會形成不可溶化層保留在該電 10 極上。 本發明更得知另一污染源會在霧化之後發生，其中在 一 E H D處理腔室内的背景氣體分子會與液體射束細滴結合 來造成酸性物質而形成表面殘留物。 不論該污染源為何，被污染物的EHD喷灑液體（或於此 15 可互換地稱為溶液）會將不良的殘留雜質留在該EHD喷灑 溶液所要清潔的每一基材上。如第2圖中所示，含帶著分開 的污染分子22之細滴20會蒸發並縮小尺寸，該等分子22會 聚結成一非揮發性的奈米團24。當該細滴進一步地蒸發 時，該奈米團24會被釋放而撞擊基材26並留存其上成為表 20 面殘留污染物28。 依據本發明之一特徵，一系統30之一實施例會產生一 多重充電的電喷灑射束其係由具有奈米和微米尺寸之細滴 所組成，而具有減少的表面殘留污染物，乃被示於第3圖。 一帶電的細滴射束3 2係藉由一密封的加壓貯槽3 6沿一毛細 10 200917348 管38輸送一導電溶液34至其一端或末梢40(以下稱為喷嘴） ' 而來產生，該噴嘴具有一小孔，較好直徑約在25〜ΙΟΟμιη 的範圍内，更好約在25至50μπι之間。該末梢40、毛細管38 和會在一霧化區中界定一電場的抽取電極3 7等係被統稱為 5 一 EHD細滴源3 9。 典型地，該溶液34可為一有機或無機的溶液混合物， 而藉添加會賦予電解活性的化學劑，例如酸類或鹼類，來 被製成導電的。該電喷灑流體可由一單成分的有機或無機 「 液體或一或多種化學性不同的成分之混合物來構成。電喷 10 灑液體之例包括但不限於：過氧化氫，ΤΜΑΗ，硝酸，磷 酸，氫氟酸，及氫氧化銨。許多上述的化學物可被以許多 方式組合來製備足以產生穩定的EHD射束之溶液混合物。 在某些用途中，該液體的導電性可能會太低或太高而不能 達到粒子大小和速度等所需的射束性質。於此等情況下， 15 所添加的酸性或驗性化學劑之量會被增加或減少而來達到 所需的射束性質。導電性添加劑亦可包括揮發性的鹽類(例 I ’ 如乙酸鐘）。 該溶液會藉施加電壓於一浸入該溶液34中的導電（金 屬、碳）導線或電極42而被充電。在該貯槽36中的溶液上方 20 施加由氣體源44所供應且被壓力/流量控制器46所調制的 壓力，將會使該溶液流經該毛細輸送管38。當抵達被納裝 在一由一真空封殼52所界定的EHD處理腔室50内之喷嘴40 處時，該溶液混合物會在霧化區54受到一由抽取電極37等 所界定的高電場，其會散佈該帶電液體而造成一束的電喷 11 200917348 灑，微米和次微米尺寸的細滴32等。如下所述，假使在使 =4羞置30的表面清潔操作期間不能避免殘留污染（瑕疵) 成於‘I&基材56_L，則溶液電解質的前噴灑管理和該射 束環境的後喷灑管理乃可有利地使之最少化。 5 依據本發明之一特徵，容裝於該貯槽36中的溶液34可 =超純的’而具有PPb(十億分之一）或更低濃度水準的雜 "適田的初始溶液包括由J. T. Baker公司以ULTREX商標 銷售的化學溶液’可被與其它的溶液及/或電解質混合來作 為該貯槽36中的溶液34。 又依據本發明之一特徵，該貯槽36是由低微粒脫落及 化學阻抗性材料所構成，包括pFA，tefl〇n，，玻 璃和類似物等。而且，該裝置30包含一處理系統57，其在 第3圖的實施例中包含一循環泵58會較好是持續地泵抽溶 液34通過一除氣腔室或除氣器60及一同軸的過濾、單元62， 15其具有一不大於0.01^m左右的濾除規格。該過濾單元62會 將被過濾且除氣後的溶液送回該貯槽36。該除氣器可由 EHD處理溶液消除被溶解的氣體，其會形如細滴/微粒成核 的前身質。在使用點譬如緊在該毛細管38的入口之前或在 該喷嘴40的毛細管出口處，以高體積流率地固定回收溶液 20將能緊在噴灑處藉EHD噴灑而使用低體積流量之前來最少 化微粒和所溶解氣體的縱跡。優點會在該回收迷率超過濾 使用速率或對該喷嘴的流率時呈現。例如，就—單獨的喷 嘴實施例而言，該回收可係為毫升/分等級。而該使用率可 係為微升/分等級。 12 200917348 能被該除氣器由該溶液排除之非唯獨的氣體之側乃包 括COx，SOx和ΡΟχ。該等氣體會分別導致石複酸、硫酸和 磷酸的形成，在該氣相時會造成酸性奈米細滴其傾向於具 有較長的蒸發時間（例請參閱Y. Ye等人之 5 Condensation-Induced Particle Formation During Vacuum200917348 IX. DESCRIPTION OF THE INVENTION: FIELD OF THE INVENTION The present invention relates generally to an apparatus and method for cleaning a surface, and more particularly to removing organic films, particulate matter and other contaminants from the surface of a semiconductor wafer. And those with reduced residual impurities and contaminants. I: Prior Art 3 Background of the Invention Since nano-scale configurations have become standard specifications in semiconductors, MEMS, memory, first-in-package, and other technical fields, new technologies have been developed to address removal by important surfaces. Problems with submicron contaminants. Electrohydrodynamics (EHD) can cause velocity-controlled nano-droplets that exhibit properties that are particularly suitable for such cleaning challenges. Electrohydrodynamic atomization involves the use of a conductive body that is broken up and dispensed into a charged nanodroplet bundle. To create an EHD beam for 15 , an electrostatic stress is applied to the liquid column surface of the conductive fluid, which exceeds the surface tension that maintains the surface intact. In a typical EHD system, a small fluid sump will contain a conductive processing chemical fluid to be sprayed, and an electrical contact in the sump will be electrically located in the fluid. A gas pressure controller applies a controlled pressure to the fluid in the 20 sump, causing a fluid flow from the sump through a capillary and into an electrostatic field at the spray end (or actual nozzle) of the capillary. The generation of EHD nanodroplets is electrically controlled by the degree of charge of the sump and the electric field manipulation at the nozzle. The speed and size of the nanodroplets can be varied to create a wide range of process settings to match the nanodroplets to contaminants and substrates such as 200917348. Nanoseed droplets can be created for the ideal coupling of momentum transfer to the particles. The EHD apparatus and method have been disclosed in U.S. Patent No. 6,033,484, the disclosure of which is incorporated herein by reference in its entirety the entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire all The name is “Method and apparatus for cleaning contaminated surfaces using strong bunches” (Mahoney), the entire contents of which are attached here. Examples of conventional electric spray liquids include water, alcohols (methanol, 2-propane). Alcohol (IPA), ethanol), glycerin, amine, η-fluorenyl B ratio 1^_(NMP), and sulfuric acid. Although EHD spray liquid solution can effectively clean the surface and substrate, at 10 the nozzle is exposed Precursor solids or gaseous impurities that are present in the solution prior to the formation are trapped and distributed after the droplets are formed. When impacting a substrate or surface, droplets that collapse due to fragmentation and evaporation are released Impurities contained in the belt cause a poor source of contamination. Also, certain compounds in the electrode/electrolyte chemistry can also cause the formation of non-15 volatile molecular species that will flow downstream to the nozzle. Being contained in the atomization zone Another source of contamination is the contaminant produced by the process resulting from the interaction of the droplets with the "background" gas and the substrate material. If the substrate material is a wafer, then "瑕疵A mapping device such as a KLA-Tensor SP2 will show that the EHD beam will cause a "light spot" (LPD) attributable to the above-mentioned sources of contamination. Accordingly, there is a need to provide an improved EHD spray solution apparatus and method for cleaning surfaces that minimizes residual surface impurities, including those formed by precursor solids or gaseous impurities in the spray solution prior to atomization. , and 200917348 due to the interaction of background gas and substrate materials due to beam droplets and the like. SUMMARY OF THE INVENTION The present invention relates to a system and method for removing surface contamination by electrospraying droplets of water, with fewer residual contaminants attributable to the droplets themselves. The system and method can be used to clean surfaces, or even to structure, etch or coat such surfaces. In one embodiment, the system includes a source configured to generate a bunch of beams on the surface, the source having an opening, a feed system configured to feed a liquid to the opening, and A 10 processing system is configured to remove impurities from the liquid. The source includes a device configured to generate an electric field to apply an electrostatic force that is higher than a surface tension of the liquid at the opening. In a more detailed embodiment of the invention, the processing system includes a degasser for venting gas from the liquid. A filter is used to remove particulates from the liquid discharge 15 and a pump is used to circulate the liquid between the feed system and the processing system. Further, the feed system includes a sump comprised of a low particle shedding and L chemically resistive material, and the pump circulates the liquid at a high volumetric flow rate that exceeds the open flow rate. In another more detailed embodiment, the system includes an electrode that charges 20 of the liquid. According to a feature of the invention, the electrode may comprise a monoatomic metal element, a binary metal alloy, a ternary metal alloy, a quaternary metal alloy, and/or glassy carbon, and selected between the electrodes The chemicals associated with the liquid can result in the formation of different species that can be effectively treated by the processing system to reduce residual surface contaminants attributable to the electrospray liquid. A method of the present invention includes providing a source head configured to generate a bunch of beams from an opening, feeding a liquid to the opening, and removing impurities from the liquid, wherein the source generates an electric field to apply The electrostatic force of the surface tension of the liquid at the opening 5 is higher. In a detailed embodiment of the invention, removing impurities from the liquid comprises degassing the liquid. The liquid is filtered and the liquid is circulated through a degasser and a filter. Moreover, the present invention comprises a heating member comprising a housing in which the agglomerated beam is generated, providing an internal electrostatic plate adjacent to the beam to attract the ionic species in the beam, and/or near the shot The beam contributes to the condensation of the gaseous species within the beam. In a more detailed embodiment of the invention, the envelope can be heated to at least 150 ° C for at least 30 minutes and the panel can be cooled at a low temperature to promote condensing. Further, the liquid chemical and a charging electrode can be selected such that the oxidation reaction at the electrode 15 results in the formation of a gaseous product or an insoluble layer which remains on the electrode without entering the solvent. The polarity of the voltage applied to the electrode also affects the species being formed. These and other features, advantages, and the like of the present invention will become more apparent from consideration of the appended claims. It should be understood that the structure and features of the alternatives are not shown in some drawings and provide a better view of the remaining structures and features. BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 shows the electrochemical reaction between a solution and an electrode in a tank in an EHD system. 200917348 Figure 2 shows a nano-aggregation formed by ρττΤΛ 4+ ik field-EHD beam droplets. Figure 3 is a view of a system in accordance with the present invention. The picture of the younger brother 3a is ~ 千立同-山不思图~ The embodiment of the change of the 依据 system according to the present invention. 5 [Implementation of Cold Mode] DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT The present invention recognizes that one source of contamination prior to atomization of an EHD spray solution includes droplets containing separate contaminating molecules that are introduced into the EHD via a variety of sources. The solution includes the contaminated initial solution and particles that are detached from the EHD-packed/deficient member and the pipe. The present invention also teaches that another source of contamination prior to atomization includes chemical interaction between the liquid to be sprayed and the electrode to which the voltage is applied and the reading solution is charged. As shown in Fig. 1, a solution 1 doped with a conductive additive AC is applied to an electrolytic cell or an insulated storage tank 12. Adjacent paired molecules 15 AC will be present in the solution as undecomposed electrolyte or solute molecules which will form an anionic-cation pair. Adjacent paired molecules are decomposed into solution anion A and solution anion, which are all dependent on the specific chemical of the additive ac and the polarity of the immersed charging electrode 14, and can interact with the material of the electrode]Vi to form New molecular MA or MC. 20 If the new molecules are a volatile gas species, the molecules will rise above the solution harmlessly and can be pumped out, but if the electrode/solution chemistry produces a non-volatile The new molecules of the species are then transported by the solution to the nozzle to provide a poor source of contamination in the electrospray droplets. These non-volatile contaminants are deposited on the substrate, which intercepts 200917348 downstream of the beam in the atomization zone. For example, if the electrode material Μ is gold, the conductive additive is hydrochloric acid (HC1), and the gold electrode is connected to a positive voltage source, the AuCl molecular species will be electrolyzed between the electrode and the conductive additive. The reaction is produced, and its coalescence in the fine droplets will form AuCl nanoclusters, 5 which will freely migrate after the jetted droplets evaporate. Other electrode/electrolyte chemistry can result in the formation of non-volatile, insoluble species that will form an insoluble layer that remains on the electrode without entering the solution. For example, if the electrode is silver and the conductive additive is HCl, a molecular species, AgCl, is formed which will form an insoluble layer remaining on the electrode. The present invention further recognizes that another source of contamination can occur after atomization, wherein background gas molecules within an E H D processing chamber combine with liquid beam droplets to cause acidic species to form surface residues. Regardless of the source of the contamination, the EHD spray liquid contaminated with the contaminants (or interchangeably referred to herein as a solution) will leave undesirable residual impurities on each substrate to be cleaned by the EHD spray solution. As shown in Figure 2, the fine droplets 20 containing the separated contaminating molecules 22 will evaporate and shrink in size, and the molecules 22 will coalesce into a non-volatile nanoparticle 24. When the fine droplets are further evaporated, the nanotubes 24 are released to strike the substrate 26 and remain thereon as surface residual contaminants 28. In accordance with one feature of the present invention, an embodiment of a system 30 produces a multi-charged electrospray beam that is comprised of fine droplets having nanometer and micron dimensions with reduced surface residual contaminants. It is shown in Figure 3. A charged fine droplet beam 3 2 is produced by transporting a conductive solution 34 along a capillary 10 200917348 tube 38 to a one end or tip 40 (hereinafter referred to as a nozzle) by a sealed pressurized storage tank 36. The nozzle has a small aperture, preferably in the range of about 25 to ΙΟΟμηη, more preferably about 25 to 50 μm. The tip 40, the capillary 38, and the extraction electrode 3 7 which defines an electric field in an atomization zone are collectively referred to as a 5-HD E droplet source 39. Typically, the solution 34 can be an organic or inorganic solution mixture which is made electrically conductive by the addition of a chemical agent which imparts electrolytic activity, such as an acid or a base. The electrospray fluid may be composed of a single component organic or inorganic "liquid or a mixture of one or more chemically different components. Examples of electrospray 10 sprinkling liquids include, but are not limited to, hydrogen peroxide, helium, nitric acid, phosphoric acid. , hydrofluoric acid, and ammonium hydroxide. Many of the above chemicals can be combined in many ways to prepare a solution mixture sufficient to produce a stable EHD beam. In some applications, the conductivity of the liquid may be too low or Too high to achieve the desired beam properties such as particle size and speed. In these cases, the amount of 15 added acidic or anatory chemicals will be increased or decreased to achieve the desired beam properties. The conductive additive may also include a volatile salt (e.g., an acetic acid clock). The solution is charged by applying a voltage to a conductive (metal, carbon) wire or electrode 42 immersed in the solution 34. Above the solution 20 in the sump 36 applies a pressure supplied by the gas source 44 and modulated by the pressure/flow controller 46 which will cause the solution to flow through the capillary delivery tube 38. When arrived, it is contained in a When the vacuum enclosure 52 defines the nozzle 40 in the EHD processing chamber 50, the solution mixture will be subjected to a high electric field defined by the extraction electrode 37 or the like in the atomization zone 54, which will spread the charged liquid. A bundle of EFI 11 200917348 sprinkles, micron and sub-micron-sized fine droplets 32, etc. As described below, it is impossible to avoid residual contamination (瑕疵) in the surface cleaning operation of making =4 shame 30. The material 56_L, the pre-spray management of the solution electrolyte and the post-spray management of the beam environment can advantageously be minimized. 5 According to one feature of the invention, the solution 34 contained in the sump 36 can be super Pure 'and the PPb (parts per billion) or lower level of mixed " Optima's initial solution including the chemical solution sold by JT Baker under the ULTREX trademark' can be combined with other solutions and / or electrolytes Mixed as a solution 34 in the sump 36. According to another feature of the invention, the sump 36 is comprised of low particle shedding and chemically resistive materials, including pFA, tefl〇n, glass and the like. , the device 30 A processing system 57 is included which, in the embodiment of FIG. 3, includes a circulation pump 58 which preferably continuously pumps the solution 34 through a degassing chamber or deaerator 60 and a coaxial filter, unit 62, 15 having a filtration specification of not more than about 0.01 μm. The filtration unit 62 returns the filtered and degassed solution to the storage tank 36. The deaerator can remove dissolved gas from the EHD treatment solution, It will be shaped like a fine droplet/particle nucleation precursor. The use of a point such as immediately before the inlet of the capillary 38 or at the capillary outlet of the nozzle 40, the recovery solution 20 will be fixed at a high volume flow rate. The EHD spray is used to minimize the microscopic and dissolved gas traces before using low volume flow. The advantage will be presented when the recovery rate exceeds the filtration usage rate or the flow rate to the nozzle. For example, in the case of a separate nozzle embodiment, the recovery can be in milliliters per minute. The usage rate can be as follows. 12 200917348 The side of the non-exclusive gas that can be excluded from the solution by the degasser is COx, SOx and helium. These gases will cause the formation of tartaric acid, sulfuric acid and phosphoric acid, respectively, which will cause acid nanodroplets to tend to have longer evaporation times (see, for example, Y. Ye et al. 5 Condensation- Induced Particle Formation During Vacuum
Pump Down,” J. Electrochem. Soc. 140, 1463,（1993)) ° 為達到該EHD細滴源39，該溶液34會經由該毛細管38 離開該貯槽36並被輸送至該噴嘴4〇。通過該毛細管的溶液 流會被該控流器46使用來自氣體源44的氣體，例如乾燥的 ίο超純氮氣來調節。-介於該氣體源44與該控流器46的入口 之間的過滤器66會由該氣體除去微粒，且一在該控流器出 口處的第二過濾H68會阻止可能源自該控流器或氣體源中 的微粒進入該貯槽36。 15 20 合禋頰型的污染種物，包括非揮 性種物’能被以如下所_電極/料（包括電解質）組合 化學物來避免： a_溶液和電崎料餘選成會使在該電極處的氧化 應導致氣體錢的形成，其會场至該溶㈣表面並被 無害地果除。該等溶液和電極材料之例為過: 化物，包括過氧化氫，並會與— 酸和乙酸等鄭若有一正合，包括餐、; ，、仕田右有一正極性施加於一 ^ 夠在-極性溶劑例如水或甘油中分解。於一實施中，丨 如’該酸係為確酸。 ’彳 b.溶液和電極被選齡使在該電極處的氧⑹ 13 200917348 應導致不可溶解層的形成，其會保留在該電極上而不進入 該溶液中。任何適當的酸皆可被使用，其係能在一極性溶 劑中分解來形成帶電離子，它們能夠形成一種具有該電極 之金屬的鹽類，其乃不可溶於該極性溶劑中。該電極係為 5 任何能夠形成一種具有一不可溶於一極性溶劑中之分解的 酸離子之鹽類的金屬。例如，當有HC1存在時使用一銀電極 會在具有正極性的電極處導致氣化銀(Ag C1)的形成，其係 不能溶於水或異丙醇(IPA)中。 該導電的電極可由不同的材料構成，包括但不限於： 10 a.—種單原子的金屬元素，例如金、銀、钽、#白； b. 任何金屬合金，包括但不限於二元、三元、和四元 的金屬合金；及 c. 玻璃狀碳。 如精習於該領域者所瞭解，電極、溶液及/或電解質的 15 選擇可被選成能避免經由不要的化學反應而產生雜質。 又，藉著施加一負電壓而非一正電壓來供電該電極，將可 得到用以產生氣體或不可溶種物的其它化合物。而且，如 上所述之藉使用一浸入電極控制電化學活性來減少該溶液 中的污染物之方法大致亦可同樣應用於導電毛細管。在一 20 如第3a圖所示之EHD裝置的實施例中，一金屬的毛細管38a 可免除一浸入的電極。 依據本發明，該當達到該喷嘴40時可供電喷灑的溶液 應要符合以下標準： 14 200917348 成分 濃度規格 鹽鹽 酸酸屬 硫磷金 不大於約20ppb ; 不大於約lOppb ;及/或 不大於約0.lppb。 因為在一EHD處理腔室中的背景氣體分子會與液體射 束細滴結合來造成酸性材料而導至表面殘留物，本發明的 5 裝置和方法會在該E H D喷灑之前和開始之後最少化背景氣 體。如第3圖所示，該EHD處理腔室50係由一真空封殼32所 界定，其中來自該貯槽的溶液於當增加該貯槽中的溶液上 方之壓力時將會經由該毛細管被輸送，該腔室具有加熱構 件可供加熱該封殼結構，及在該腔室内部的冷却面板等以 10 便冷凝由該電噴灑液體上升之不要的氣體種物而來收集。 在所示實施例中，加熱帶70係被置設於該封殼外部以加熱 該封殼結構。又，低溫冷却的面板72等會以大致包圍的構 形圍繞該霧化區54被置設在該封殼内部而靠近於該電喷灑 射束32。 15 依據本發明，一種處理一EHD處理腔室以減少基材表 面殘留污染物的方法包括： Α.將該EHD處理腔室50的封殼結構52加熱至一大約 150°C的溫度歷經一大約30分鐘以上的時間，而來除氣和淨 化該腔室50之内表面壁和内部處理構件等。 20 B.施加電壓於該等靜電板73以加強由射束細滴產生之 離子種物的靜電收集。 C.提供該腔室50内的冷却表面以藉由冷凝來進一步協 15 200917348 助捕捉由射束細滴產生之不要的氣體種物。 ，二：喿作情況下’動作A、一係在噴嘴開始電 5 10 15 20 動〜為有效，作 以上說明已參照本發明 熟習哕仙月古關士义 目刖車父佳的實施例來呈現0 :麵域及㈣本發明所屬技術之卫作者將會 所述結構中的修改和變化亦 ' ’、在 之原理、精神及範圍。破實她而不實質超出本發明 附圖式二==不=解讀為僅限於所述及被示*所 圚式中的精細結構’而應被 的申請專職圍，其似有於並4持以下 I：圖式簡單說明之最元整且公平的範圍。 第1圖示出在一EHD系統 核之間的電化學反應。I叫 幻圖示出由一獅射束細滴形成-奈米聚團。 第3圖為一示意圖示出—依 第3a圖為一示意圖示出= 發明的系統之實 施例。 依據本發明㈣統之變化實 【主要元件符號說明】 1〇.··溶液 12.. •貯槽 14，42...電極 2〇..·細滴 22.·.污染分子 24…奈米團 28.··表面殘留污染物 16 200917348 30...系統 56".標把基材 32...細滴射束 57...處理系統 34...導電溶液 58...循環泵 36...加壓貯槽 60...除氣器 37...抽取電極 62...過滤單元 38...毛細管 66，68...過滤器 39...EHD細滴源 70...加熱帶 40…喷嘴 72...面板 44...氣體源 73...靜電板 46...控制器 A…溶液陰離子 50...EHD處理腔室 AC...導電添加劑 52...真空封殼 C...溶液陽離子 54...霧化區 M...電極材料 17Pump Down,” J. Electrochem. Soc. 140, 1463, (1993)) ° To reach the EHD fine droplet source 39, the solution 34 exits the sump 36 via the capillary 38 and is delivered to the nozzle 4〇. The solution stream of the capillary is regulated by the flow controller 46 using a gas from a gas source 44, such as dry ίο ultrapure nitrogen. - a filter between the gas source 44 and the inlet of the flow controller 46 66 will remove particles from the gas, and a second filter H68 at the outlet of the flow block will prevent particles from the flow controller or gas source from entering the sump 36. 15 20 Contamination of the buccal type Seeds, including non-volatile species, can be avoided by combining chemicals with the following: electrode/material (including electrolyte): a_solution and electroslag are selected so that oxidation at the electrode should result in gas The formation of money, the site to the surface of the dissolved (four) and is harmlessly removed. Examples of such solutions and electrode materials are: compounds, including hydrogen peroxide, and will be positively associated with - acid and acetic acid , including meals,;,, Shi Tian right has a positive polarity applied to a ^ enough in - polarity Decomposition in a solvent such as water or glycerol. In one embodiment, for example, the acid is an acid. '彳b. The solution and the electrode are selected to make the oxygen at the electrode (6) 13 200917348 should result in the formation of an insoluble layer It will remain on the electrode without entering the solution. Any suitable acid can be used which decomposes in a polar solvent to form charged ions which are capable of forming a salt of a metal having the electrode. It is insoluble in the polar solvent. The electrode is 5 any metal capable of forming a salt having a decomposed acid ion which is insoluble in a polar solvent. For example, a silver is used when HC1 is present. The electrode can cause the formation of vaporized silver (Ag C1) at the electrode having positive polarity, which is insoluble in water or isopropyl alcohol (IPA). The conductive electrode can be composed of different materials including, but not limited to: 10 a. - a single atomic metal element, such as gold, silver, iridium, #白; b. any metal alloy, including but not limited to binary, ternary, and quaternary metal alloys; and c. glassy carbon As in the collar As the domain knows, the choice of electrode, solution and/or electrolyte can be chosen to avoid impurities generated by unwanted chemical reactions. Again, by applying a negative voltage instead of a positive voltage, the electrode can be powered. Other compounds are used to generate gas or insoluble species. Moreover, the method of reducing the contaminants in the solution by using an immersion electrode to control the electrochemical activity as described above can be applied to the conductive capillary as well. 20 In the embodiment of the EHD device shown in Fig. 3a, a metal capillary 38a can dispense with an immersed electrode. According to the present invention, the solution that can be powered for spraying when the nozzle 40 is reached should meet the following criteria: 200917348 Component concentration specification salt hydrochloric acid thiophosphoric acid is not more than about 20 ppb; not more than about 10 ppb; and / or not more than about 0.1 ppb. Since the background gas molecules in an EHD processing chamber combine with the liquid jet droplets to cause acidic material to lead to surface residues, the 5 apparatus and method of the present invention minimizes before and after the EHD spraying. Background gas. As shown in FIG. 3, the EHD processing chamber 50 is defined by a vacuum envelope 32, wherein a solution from the sump is delivered via the capillary when the pressure above the solution in the sump is increased. The chamber has a heating member for heating the envelope structure, and a cooling panel or the like inside the chamber collects the gas species that are raised by the electric spray liquid to collect the gas species. In the illustrated embodiment, a heating belt 70 is disposed external to the enclosure to heat the enclosure structure. Further, the subcooled panel 72 or the like is placed around the atomization zone 54 in the substantially enclosed configuration adjacent to the electrospray beam 32. 15 In accordance with the present invention, a method of treating an EHD processing chamber to reduce residual contaminants on a substrate surface comprises: 加热 heating the enclosure structure 52 of the EHD processing chamber 50 to a temperature of about 150 ° C. For more than 30 minutes, the inner surface wall and the inner processing member of the chamber 50 are degassed and purified. 20 B. Apply voltage to the electrostatic plates 73 to enhance electrostatic collection of ionic species produced by the beam droplets. C. Providing a cooling surface within the chamber 50 to further capture the unwanted gas species produced by the beam droplets by condensation. 2: In the case of the operation, 'action A, one system starts at the nozzle 5 10 15 20 movements~ is valid, and the above description has been presented with reference to the embodiment of the invention familiar with the 哕仙月古关士义目刖车佳佳: AREAS AND (IV) EMBODIMENT OF THE EMBODIMENT OF THE INVENTION The modifications and variations in the described structure are also in the principles, spirit, and scope. She is not actually beyond the scope of the present invention. ====================================================================================== The following I: The schema is a simple and fair range. Figure 1 shows the electrochemical reaction between the cores of an EHD system. I called the phantom showing a droplet formed by a lion beam - a nano cluster. Fig. 3 is a schematic view showing an embodiment of the system of the invention according to Fig. 3a. According to the invention (4) changes in the system [main components symbol description] 1 〇.··solution 12:. Storage tank 14, 42... electrode 2 〇..·fine droplets 22.·. Contaminant molecules 24... nano-group 28.··surface residual contaminants 16 200917348 30...system 56".bar substrate 32...fine droplet beam 57...processing system 34...conductive solution 58...circulation pump 36. ..Pressure tank 60...Deaerator 37...Extraction electrode 62...Filter unit 38...Capillary 66,68...Filter 39...EHD fine droplet source 70...plus Tropical 40...nozzle 72...panel 44...gas source 73...electrostatic plate 46...controller A...solution anion 50...EHD processing chamber AC...conductive additive 52...vacuum Enclosure C... Solution Cation 54...Atomization Zone M...Electrode Material 17