TWI692011B - Method for neutral beam processing based on gas cluster ion beam technology and articles produced thereby - Google Patents

Method for neutral beam processing based on gas cluster ion beam technology and articles produced thereby Download PDF

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TWI692011B
TWI692011B TW105122882A TW105122882A TWI692011B TW I692011 B TWI692011 B TW I692011B TW 105122882 A TW105122882 A TW 105122882A TW 105122882 A TW105122882 A TW 105122882A TW I692011 B TWI692011 B TW I692011B
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gcib
neutral
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gas cluster
neutral beam
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TW201804521A (en
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席恩R 柯克派翠克
理察C 什夫盧加
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美商艾克索傑尼席斯公司
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A method of forming a patterned hard mask on a surface of a substrate uses an accelerated neutral beam with carbon atoms.

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用於基於氣體簇離子束技術的中性束處理之方法及藉其製造之物件 Method for neutral beam treatment based on gas cluster ion beam technology and articles manufactured therefrom 發明領域 Field of invention

本發明廣泛關於一種用於低能量、中性束處理之方法及設備;及更特別關於一種用以從經加速的氣體簇離子束取得經加速的中性單體及/或中性氣體簇束之高束純度方法及系統,其係用以處理使用來製造積體電路之基材。 The present invention relates broadly to a method and apparatus for low energy, neutral beam processing; and more particularly to a method for obtaining accelerated neutral monomers and/or neutral gas cluster beams from accelerated gas cluster ion beams A high-beam purity method and system for processing substrates used to manufacture integrated circuits.

發明背景 Background of the invention

在過去十年間,氣體簇離子束(GCIB)已變熟知及廣泛使用於多種表面及次表面處理應用。因為氣體簇離子典型具有大質量,甚至當加速至實質能量時,它們趨向於以相對低的速度(與習知離子比較)行進。這些低速度與該簇之固有的弱黏結結合產生獨特的表面處理能力,與習知的離子束及擴散電漿比較,此導致減低表面滲透及減低表面損傷。 Over the past decade, gas cluster ion beam (GCIB) has become well known and widely used in a variety of surface and subsurface treatment applications. Because gas cluster ions typically have a large mass, even when accelerated to substantial energy, they tend to travel at a relatively low speed (compared to conventional ions). These low velocities combine with the inherent weak bonding of the cluster to produce a unique surface treatment capability, which results in reduced surface penetration and reduced surface damage compared to conventional ion beams and diffusion plasmas.

已經使用氣體簇離子束來平滑化、蝕刻、清潔、在上面形成沈積物、在上面生長膜或其它方面修改廣 泛多種表面,包括例如金屬、半導體及介電材料。在包括半導體及半導體相關材料的應用中,已經使用GCIBs來清潔、平滑化、蝕刻、沈積及/或生長膜包括氧化物及其它。亦已使用GCIBs來引進摻雜及晶格變形原子物種、用以非晶相化表面層及改良摻雜物在半導體材料中的溶解度之材料。在許多情況中,此GCIB應用已經能夠提供優於使用習知離子、離子束及電漿之其它技術的結果。該半導體材料包括廣泛範圍能藉由引進摻雜材料來操控電性質的材料,及包括(非為限制)矽、鍺、鑽石、碳化矽,及亦包括包含III-IV族元素及II-VI族元素的化合物材料。因為使用氬(Ar)作為來源氣體容易形成GCIBs及因為氬的惰性性質,已經發展出使用氬氣GCIBs來處理可植入式醫療裝置表面的許多應用,諸如冠狀動脈血管支架、矯形假體及其它可植入式醫療裝置。在半導體應用中,已經使用多種來源氣體及來源氣體混合物來形成包括電摻雜物及晶格變形物種的GCIBs,而用於反應性蝕刻、物理性蝕刻、膜沈積、膜生長及其它有用的製程。已知曉多種將GCIB處理引進廣泛範圍的表面型式之可實行系統。例如,由Kirkpatrick等人發佈的美國專利6,676,989 C1教導一種具有適合於處理管狀或圓柱狀工件諸如血管支架之工件座及操縱器的GCIB處理系統。在另一個實施例中,Kirkpatrick等人發佈的美國專利6,491,800 B2教導一種具有用以處理其它非平面醫療裝置型式包括例如髖關節假體之工件座及操縱器的GCIB處理系統。進一步實施例,Libby等人發佈的 美國專利6,486,478 B1教導一種合適於處理半導體晶圓之自動化基材負載/卸載系統。Hautala發佈的美國專利7,115,511教導相對於非掃描式GCIB,其使用機械式掃瞄器係來掃描工件。在又另一個實施例中,Blinn等人發佈的美國專利7,105,199 B2教導使用GCIB處理來改良藥物塗層在醫療裝置上的黏附力及修改藥物從該醫療裝置溶析或釋放出的速率。 Gas cluster ion beams have been used to smooth, etch, clean, form deposits on, grow films on, or otherwise modify a wide range A wide variety of surfaces, including, for example, metals, semiconductors, and dielectric materials. In applications including semiconductors and semiconductor-related materials, GCIBs have been used to clean, smooth, etch, deposit, and/or grow films including oxides and others. GCIBs have also been used to introduce doping and lattice deforming atomic species, materials for amorphous phased surface layers, and improved solubility of dopants in semiconductor materials. In many cases, this GCIB application has been able to provide results that are superior to other techniques using conventional ions, ion beams, and plasma. The semiconductor materials include a wide range of materials that can control the electrical properties by introducing doped materials, and include (but are not limited to) silicon, germanium, diamond, silicon carbide, and also include group III-IV elements and group II-VI Elemental compound material. Because the use of argon (Ar) as the source gas easily forms GCIBs and because of the inert nature of argon, many applications have been developed that use argon GCIBs to treat the surface of implantable medical devices, such as coronary stents, orthopedic prostheses, and others Implantable medical device. In semiconductor applications, a variety of source gases and source gas mixtures have been used to form GCIBs including electrical dopants and lattice deforming species for reactive etching, physical etching, film deposition, film growth, and other useful processes . A variety of practicable systems have been known to introduce GCIB processing into a wide range of surface types. For example, US Patent 6,676,989 C1 issued by Kirkpatrick et al. teaches a GCIB processing system with a workpiece holder and manipulator suitable for processing tubular or cylindrical workpieces such as vascular stents. In another embodiment, US Patent 6,491,800 B2 issued by Kirkpatrick et al. teaches a GCIB processing system with a workpiece holder and manipulator for processing other non-planar medical device types including, for example, hip prostheses. Further examples, published by Libby et al US Patent 6,486,478 B1 teaches an automated substrate loading/unloading system suitable for processing semiconductor wafers. U.S. Patent No. 7,115,511 issued by Hautala teaches the use of a mechanical scanner system to scan a workpiece relative to a non-scanning GCIB. In yet another embodiment, US Patent 7,105,199 B2 issued by Blinn et al. teaches the use of GCIB treatment to improve the adhesion of the drug coating on the medical device and modify the rate at which the drug dissolves or is released from the medical device.

已經使用GCIB來蝕刻及平滑化結晶及非結晶形式材料,諸如鑽石及其它寶石。此尚未完全成功,因為有時寶石可由於GCIB處理而進行不想要的顏色改變。尚未清楚的是,此變色係產生自對寶石材料的某些表面或次表面之損傷形式、或可由於在產生自GCIB處理之經蝕刻及/或平滑化表面層與下面未修改的材料本體間所形成之粗糙界面、或或許由於由簇離子引發的表面電荷之損傷。諸如此的GCIB處理之負面副作用原因,想要一種未引進不想要的寶石外觀及美學訴求降低之用以蝕刻及/或平滑化天然及合成寶石材料的處理技術。已經指示出GCIB處理作為一種用以平滑化及/或平坦化光學材料諸如鏡片的表面、反射光學表面、光學窗、用於顯示器及觸控式螢幕面板的光學面板、稜鏡裝置、用於光罩及其類似物的透明基材、光波導、光電裝置及其它光學裝置的可能技術。該用於光學裝置的材料包括廣泛多種玻璃、石英、藍寶石、鑽石及其它硬的透明材料。包括機械式、化學機械式及其它技術的習知拋光及平坦化尚無法產生合適於大部分應用需 求的表面。在許多情況中,已顯示出GCIB處理能將光學表面平滑及/或平坦化至無法由習知拋光技術獲得之程度,但是需要另一種不會在該平滑表面與下面塊材間產生粗糙界面以避免產生在該光學材料中埋入散射層的技術。 GCIB has been used to etch and smooth materials in crystalline and non-crystalline forms, such as diamonds and other precious stones. This has not been completely successful because sometimes gems can undergo unwanted color changes due to GCIB treatment. It is not clear that this discoloration is caused by damage to certain surfaces or subsurfaces of the gem material, or it may be due to the etched and/or smoothed surface layer resulting from the GCIB treatment and the unmodified material body below The rough interface formed may be due to damage of surface charges caused by cluster ions. The reason for the negative side effects of GCIB treatments such as this requires a treatment technique for etching and/or smoothing natural and synthetic gem materials that does not introduce an undesirable reduction in gemstone appearance and aesthetic appeal. GCIB processing has been instructed as a method for smoothing and/or planarizing optical materials such as lens surfaces, reflective optical surfaces, optical windows, optical panels for displays and touch screen panels, prism devices, for light Possible technologies for transparent substrates, optical waveguides, optoelectronic devices, and other optical devices for covers and the like. The materials used for optical devices include a wide variety of glass, quartz, sapphire, diamond, and other hard transparent materials. Conventional polishing and planarization including mechanical, chemical-mechanical and other technologies have not yet produced suitable for most applications Seeking surface. In many cases, it has been shown that the GCIB treatment can smooth and/or flatten the optical surface to a level that cannot be obtained by conventional polishing techniques, but requires another that does not create a rough interface between the smooth surface and the underlying block to The technique of burying the scattering layer in the optical material is avoided.

雖然已經成功地將GCIB處理使用於許多應用,尚有未由GCIB或技藝方法及設備的其它狀態完全滿足之新及現存的應用需求。在許多狀況中,雖然GCIB可產生初始稍微粗糙之引人注目的原子標度平滑度之表面,但其可達成的最終平滑度經常少於所需要的平滑度,及在其它狀況中,GCIB處理可產生適度粗糙的平滑表面而非進一步平滑化其。 Although GCIB processing has been successfully used in many applications, there are new and existing application requirements that are not fully satisfied by GCIB or other state of the art methods and equipment. In many cases, although GCIB can produce an initially slightly rough surface with an atomic scale smoothness, the achievable final smoothness is often less than the required smoothness, and in other cases, GCIB treatment A moderately rough smooth surface can be produced instead of further smoothing it.

如透過本發明的具體實例之認知及分辨,亦存在有其它需求/機會。在藥物溶析(drug-eluting)式醫療植入物領域中,GCIB處理已經在醫療植入物上的藥物塗層表面處理上成功,其讓該塗層黏結至基材或修改該藥物在植入患者後從該塗層中溶析出之速率。但是,已經注意到在已經使用GCIB來處理藥物塗層(其經常非常薄及可包含非常昂貴的藥物)之某些情況中,可發生由於該GCIB處理之藥物塗層的重量損失(此象徵藥物損失或移除)。對發生此損失(某些藥物及使用某些處理參數)的特別情況來說,該事件通常不想要,及具有避免重量損失同時仍然獲得令人滿意的藥物溶析速率控制之能力的方法係較佳。 There are other needs/opportunities, such as through recognition and discrimination of specific examples of the present invention. In the field of drug-eluting medical implants, GCIB treatment has been successful on the surface treatment of drug coatings on medical implants, which allows the coating to adhere to the substrate or modify the drug in the implant The rate of leaching out of the coating after entering the patient. However, it has been noted that in some cases where GCIB has been used to treat drug coatings (which are often very thin and can contain very expensive drugs), weight loss due to the GCIB-treated drug coatings can occur (this symbolizes the drug Loss or removal). For the particular case of this loss (some drugs and the use of certain processing parameters), this event is usually undesirable and the method with the ability to avoid weight loss while still obtaining satisfactory control of the rate of drug dissolution is more good.

在半導體應用中,使用GCIBs已經在許多表面處理改良上具有不同的成功程度,但是存在有改良機會。 在習知GCIB處理中,雖然改良明顯超過早期習知技術,結果經常為其品質仍然非由大部分需求應用所需要。例如,在平滑化製程中,對許多材料來說,使用GCIB處理實際上可獲得的最後平滑度程度總是無法滿足需求。在將其它材料引進半導體材料的應用(有時稱為GCIB注入(GCIB infusion))中,為了摻雜、晶格變形及其它應用諸如膜沈積、膜生長及非晶相化的目的,於該照射層與下面基材間的界面處,在該經注入、生長、非晶相化或沈積的材料間之界面經常具有粗糙度或不均勻性,此損害該經GCIB修改的層之最理想性能。 In semiconductor applications, the use of GCIBs has had varying degrees of success in many surface treatment improvements, but there are opportunities for improvement. In conventional GCIB processing, although the improvement significantly exceeds the earlier conventional technology, the result is often that its quality is still not required by most demanding applications. For example, in the smoothing process, for many materials, the final degree of smoothness that can actually be achieved using GCIB processing cannot always meet the demand. In applications that introduce other materials into semiconductor materials (sometimes referred to as GCIB infusion), for the purpose of doping, lattice deformation, and other applications such as film deposition, film growth, and amorphous phase transformation, the irradiation At the interface between the layer and the underlying substrate, the interface between the implanted, grown, amorphous phased, or deposited material often has roughness or non-uniformity, which compromises the optimal performance of the GCIB modified layer.

離子已長時間受許多處理喜愛,因為其電荷使得其容易藉由靜電及磁場操控。此在處理時引進大彈性。但是,在某些應用中,任何離子(包括在GCIB中之氣體簇離子)固有的電荷可在經處理之表面中產生不想要的效應。GCIB具有可區別超過習知離子束的優點,其中與習知離子(單一原子、分子或分子碎片)比較,具有單一或小多重電荷之氣體簇離子能夠傳輸及控制更大的質量流(一簇可由數百或數千個分子組成)。特別在絕緣材料的情況中,使用離子處理的表面經常遭遇到產生自累積的電荷突然放電之電荷引發型損傷,或在該材料中產生電場引發的應力損傷(再次產生自累積的電荷)。在許多此等情況中,GCIBs由於其每質量相對低的電荷而具有優點,但是在某些例子中會無法消除標靶帶電問題。再者,中至高電流強度離子束可遭遇到明顯由空間電荷引發的束散焦,此趨向 於抑制在長距離內傳輸經良好聚焦的束。再次,由於其相對於習知離子束之每質量較低的電荷,GCIBs具有優點,但是它們無法完全消除空間電荷傳輸問題。 Ions have been favored by many processes for a long time because their charge makes them easily manipulated by static electricity and magnetic fields. This introduces great flexibility in handling. However, in some applications, the inherent charge of any ion (including gas cluster ions in GCIB) can produce undesirable effects in the treated surface. GCIB has the advantage that it can be distinguished over conventional ion beams. Compared with conventional ions (single atom, molecule or molecular fragment), gas cluster ions with single or small multiple charges can transmit and control a larger mass flow (a cluster (Can be composed of hundreds or thousands of molecules). Especially in the case of insulating materials, surfaces treated with ions often encounter charge-induced damage that results from a sudden discharge of accumulated charges, or stress damage caused by electric fields in the material (again from accumulated charges). In many of these cases, GCIBs have advantages due to their relatively low charge per mass, but in some cases the target charging problem cannot be eliminated. Furthermore, medium to high current intensity ion beams can encounter defocusing of the beam apparently caused by space charge. To suppress the transmission of well-focused beams over long distances. Third, GCIBs have advantages because of their lower charge per mass compared to conventional ion beams, but they cannot completely eliminate space charge transfer problems.

由於下列事實引起進一步需要或機會的例子:雖然使用中性分子或原子束可在某些表面處理應用中及在無空間電荷束傳輸中提供利益,但除了噴嘴噴射的情況外,通常不容易及經濟地產生強的中性分子或原子束,其中該能量級數通常為每原子或分子幾毫電子伏特,因此其具有有限的處理能力。 Examples of further needs or opportunities due to the following facts: Although the use of neutral molecules or atomic beams can provide benefits in certain surface treatment applications and in space-free charge beam transmission, it is generally not easy to Strongly neutral molecules or atomic beams are produced economically, where the energy level is usually a few millielectron volts per atom or molecule, so it has limited processing power.

在Hughes Electronics Corporation的美國專利4,935,623中,Knauer已教導一種用以形成高能(1至10電子伏特)帶電及/或中性原子束的方法。Knauer形成習知GCIB及在掠射角下將其導向解離該簇離子的固體表面諸如矽板,此產生前向散射的原子及習知離子束。此產生強但是未聚焦可使用於處理的中性原子及離子束,或在靜電隔離離子後可以中性原子束使用於處理。因為GCIB需要固體表面散射來產生解離,Knauer技術引進明顯的問題。遍及寬廣的束能量範圍,GCIB在其攻擊之表面中產生強的濺射。已經清楚地顯示出(參見例如,Aoki,T及Matsuo,J,”Molecular dynamics simulations of surface smoothing and sputtering process with glancing-angle gas cluster ion beams”,Nucl.Instr.& Meth.in Phys.Research B 257(2007),pp.645-648),甚至在如由Knauer使用的掠射角下,GCIBs產生相當大地固體濺射,因此該前向散射的中 性束係受源自於使用來散射/解離的固體表面之濺射離子及中性原子及其它顆粒污染。在包括醫療裝置處理應用及半導體處理應用的許多應用中,此污染該前向散射束的濺射材料之存在使得其不合適於使用。 In US Patent 4,935,623 of Hughes Electronics Corporation, Knauer has taught a method for forming high energy (1 to 10 electron volts) charged and/or neutral atomic beams. Knauer forms a conventional GCIB and directs it at a glancing angle to a solid surface that dissociates the cluster of ions, such as a silicon plate, which produces forward scattered atoms and a conventional ion beam. This produces strong but unfocused neutral atoms and ion beams that can be used for processing, or can be used for processing after electrostatically isolating ions. Because GCIB requires solid surface scattering to generate dissociation, Knauer technology introduces obvious problems. Across the wide beam energy range, GCIB produces strong sputtering in the surface it attacks. It has been clearly shown (see, for example, Aoki, T and Matsuo, J, "Molecular dynamics simulations of surface smoothing and sputtering process with glancing-angle gas cluster ion beams", Nucl. Instr. & Meth. in Phys. Research B 257 (2007), pp. 645-648), even at glancing angles as used by Knauer, GCIBs produce fairly solid sputtering, so the forward scattering Sex beams are contaminated with sputtered ions and neutral atoms and other particles that originate from the solid surface used to scatter/dissociate. In many applications, including medical device processing applications and semiconductor processing applications, the presence of this sputtered material contaminating the forward scattered beam makes it unsuitable for use.

在美國專利7,060,989中,Swenson等人教導使用具有氣體壓力高於束產生壓力之氣體壓力單元來修改在GCIB中的氣體簇離子能量分佈。該技術降低在GCIB中的氣體簇離子能量及修改此經修改的GCIBs之某些表面處理特徵。此經氣體修改的GCIB氣體簇離子能量分佈係有幫助,但是其未減少由在GCIB中的離子堆積於工件上之電荷所造成的問題,及未解決某些處理問題,如例如,藥物塗層在GCIB處理期間之重量損失。雖然Swenson等人的技術可改良GCIB之最終表面平滑特徵,但結果仍然低於理想。 In US Patent 7,060,989, Swenson et al. teach the use of a gas pressure cell with a gas pressure higher than the beam generation pressure to modify the gas cluster ion energy distribution in GCIB. This technique reduces the energy of gas cluster ions in GCIB and modifies certain surface treatment characteristics of this modified GCIBs. This gas-modified GCIB gas cluster ion energy distribution is helpful, but it does not reduce the problems caused by the charge accumulated on the workpiece by the ions in GCIB, and does not solve some processing problems, such as, for example, drug coating Weight loss during GCIB processing. Although the technique of Swenson et al. can improve the final surface smoothing characteristics of GCIB, the results are still below ideal.

氣體簇及氣體簇離子尺度典型由包含各別簇的原子或分子數目N標出特徵(依該氣體係原子或分子而定及包括變體,諸如離子、單體、二聚物、三聚物、配位基)。咸信由習知GCIB處理貢獻的許多優點係來自在GCIB中之低速度的離子及來自下列事實:該大的、鬆散束縛的簇在與固體表面碰撞時崩解造成短暫的加熱及壓力,但是對表面下之基材沒有過多的滲透、植入或損傷。此大簇(具有N個單體,如在下列定義,級數呈數千或更多)之效應通常限制至數十埃。但是,已經顯示出較小的簇(具有N之級數係數百至約一千)對衝擊的表面產生更多損傷及能 在表面中產生個別的衝擊坑洞(參見例如,Houzumi,H.等人,”Scanning tunneling microscopy observation of graphite surfaces irradiated with size-selected Ar cluster ion beams”,Jpn.J.Appl.Phys.V44(8),(2005),p 6252 ff)。此坑洞形成效應可粗糙化表面及從其移除材料(蝕刻),此與較大簇的表面平滑效應形成不想要的競爭。在已經發現GCIB係有用的許多其它表面處理應用中,咸信大氣體簇離子與較小氣體簇離子的效應可以反效果方式競爭而減低處理性能。不幸的是,容易施用以形成GCIBs的技術全部造成產生具有寬廣簇尺度分佈之束,其具有尺度N範圍係約100至多如數萬。該尺度分佈的平均及/或波峰經常位於數百至幾千的範圍內,且在該分佈的尺度極端處之分佈尾部逐漸減少至零。該簇離子尺度分佈及與分佈相關的平均簇尺度NMean係與所使用的來源氣體相依,及可明顯地由使用來形成該噴射簇的噴嘴參數之選擇、由通過該噴嘴的壓力降及由噴嘴溫度影響,此全部皆根據習知GCIB形成技術。大部分的商業GCIB處理工具例行地使用磁性或偶爾靜電尺度分離器來移除大部分損傷性最小離子及簇(單體、二聚物、三聚物等等至最高約N=10或更大)。此過濾器經常指為”單體過濾器”,然而它們典型亦移除稍微較大的離子和單體。某些靜電簇離子尺度選擇器(如例如,在美國專利4,935,623中由Knauer所使用者)需要將電導柵網放入該束中,由於該柵網可能由該束侵蝕而引進強的缺點,此將引進束污染物同時減低信賴度及產生額外維護該設備的需 求。為此理由,現在的單體及低質量過濾器典型為磁性型式(參見例如,Torti等人的美國專利6,635,883,及Libby等人的美國專利6,486,478)。除了藉由磁性過濾器有效地移除最小離子(單體、二聚物等等)外,已顯露出大部分GCIBs包括少數或無尺度低於約N=100的氣體簇離子。此可係此等尺度不容易形成或在形成後不穩定。但是,在大部分商業GCIB處理工具的束中似乎呈現出於約N=100至幾百的範圍內之簇。當使用習知技術時,通常遇到NMean值在幾百至數千的範圍內。因為對所提供的加速電壓來說,中尺度的簇之行進比較大的簇更快,它們更可能產生坑洞、粗糙的界面及其它不想要的效應,及當存在於GCIB中時,此大概促成低於理想的處理。 Gas clusters and gas cluster ion scales are typically characterized by the number N of atoms or molecules containing each cluster (depending on the gas system atoms or molecules and including variants such as ions, monomers, dimers, trimers , Ligand). Xianxin’s many advantages contributed by the conventional GCIB process come from the low-velocity ions in GCIB and from the fact that the large, loosely bound cluster disintegrates when it collides with a solid surface, causing transient heating and pressure, but There is no excessive penetration, implantation or damage to the substrate under the surface. The effect of this large cluster (with N monomers, as defined in the following, the series is thousands or more) is usually limited to tens of angstroms. However, it has been shown that smaller clusters (having a series coefficient of N from one hundred to about one thousand) produce more damage to the impacted surface and can produce individual impact pits in the surface (see, for example, Houzumi, H. Et al., "Scanning tunneling microscopy observation of graphite surfaces irradiated with size-selected Ar cluster ion beams", Jpn. J. Appl. Phys. V44 (8), (2005), p 6252 ff). This pothole-forming effect can roughen the surface and remove material from it (etching), which creates unwanted competition with the surface smoothing effect of larger clusters. In many other surface treatment applications where the GCIB series has been found useful, the effects of Xianxin's large gas cluster ions and smaller gas cluster ions can compete in a counter-effect manner to reduce processing performance. Unfortunately, the techniques that are easy to apply to form GCIBs all result in beams with a broad cluster-scale distribution, with a scale N range from about 100 to as many as tens of thousands. The average and/or peaks of the scale distribution are often in the range of hundreds to thousands, and the tail of the distribution at the scale extremes of the distribution gradually decreases to zero. The cluster ion scale distribution and the average cluster scale N Mean associated with the distribution are dependent on the source gas used, and can obviously be selected by the nozzle parameters used to form the jet cluster, by the pressure drop through the nozzle and by The influence of nozzle temperature is based on the conventional GCIB formation technology. Most commercial GCIB processing tools routinely use magnetic or occasional electrostatic scale separators to remove most of the damaging smallest ions and clusters (monomers, dimers, trimers, etc. up to about N=10 or more Big). Such filters are often referred to as "monomer filters", however they also typically remove slightly larger ions and monomers. Some electrostatic cluster ion scale selectors (such as, for example, used by Knauer in U.S. Patent 4,935,623) need to place an electrically conductive grid into the beam. Since the grid may be eroded by the beam and introduces strong disadvantages, this Beam pollutants will be introduced while reducing reliability and creating additional maintenance requirements for the equipment. For this reason, current monolithic and low-quality filters are typically of the magnetic type (see, for example, U.S. Patent 6,635,883 by Torti et al., and U.S. Patent 6,486,478 by Libby et al.). In addition to effectively removing the smallest ions (monomers, dimers, etc.) by magnetic filters, it has been revealed that most GCIBs include few or no scale gas cluster ions below about N=100. This may be because these dimensions are not easily formed or are unstable after formation. However, it seems that clusters in the range of about N=100 to several hundred appear in the bundle of most commercial GCIB processing tools. When using conventional techniques, it is often encountered that the N Mean value is in the range of hundreds to thousands. Because of the acceleration voltage provided, mesoscale clusters travel faster than larger clusters, they are more likely to produce potholes, rough interfaces, and other unwanted effects, and when present in GCIB, this is probably Contribute to sub-ideal processing.

在微電子半導體處理技術中,習知上已於形成所需要的裝置結構時使用光阻微影蝕刻來進行許多及不同圖案化步驟。已產生的一個問題為在微影蝕刻步驟後之光阻材料移除可遺留污染物(呈顆粒形式或其它方面),其可損害或危及隨後的處理步驟、減低製程產率。當裝置幾何形狀進步至較小尺度時,微粒狀污染物變成更明顯的問題。再者,伴隨著要達成較小裝置構形的進行性需求,已顯露出使用光阻微影蝕刻的其它問題。不斷需要較薄的光阻層(少於50奈米厚)來對付光阻圖案塌陷之問題,及必需因應較短波長包括X射線波長而修改該光阻材料。為了因應此挑戰,考慮到不需要將光阻基底的微影蝕刻使用於先進的半導體處理之圖案化技術變重要。已經使用聚焦的離 子束技術作為替代技術。亦使用開口圖案樣板(亦指為模板或孔罩),其可以接觸式圖案化樣板或以投射式圖案化樣板使用。此等遮罩、模板或樣板於本文中全部指為”樣板”。因為中性束技術形成極淺表面層之能力,其對先進的半導體處理技術具有特別的可應用性,其特別合適於使用樣板進行處理來控制非常小、非常淺的半導體結構之圖案化而形成先進的結構。因此,本發明的目標為提供一種用以形成用於工件處理之高純度中性氣體簇束的設備及方法。 In microelectronic semiconductor processing technology, conventionally, photoresist lithography has been used to form many and different patterning steps when forming a desired device structure. One problem that has arisen is that the removal of photoresist material after the lithography etching step can leave contaminants (in the form of particles or otherwise), which can damage or endanger subsequent processing steps and reduce process yield. As device geometry advances to smaller scales, particulate contaminants become a more obvious problem. Furthermore, along with the ongoing need to achieve smaller device configurations, other problems with photoresist lithography have been revealed. Thinner photoresist layers (less than 50 nanometers thick) are constantly needed to deal with the problem of photoresist pattern collapse, and the photoresist material must be modified in response to shorter wavelengths including X-ray wavelengths. In order to meet this challenge, it is considered that patterning techniques that do not require photolithographic etching of photoresist substrates for advanced semiconductor processing become important. Focused focus Sub-beam technology as an alternative technology. Open pattern templates (also referred to as templates or perforated covers) are also used, which can be used in contact pattern patterns or in projection pattern patterns. These masks, templates or templates are referred to herein as "templates". Because of its ability to form a very shallow surface layer, the neutral beam technology is particularly applicable to advanced semiconductor processing technology, and it is particularly suitable for processing using a template to control the patterning of very small and very shallow semiconductor structures. Advanced structure. Therefore, an object of the present invention is to provide an apparatus and method for forming a cluster of high-purity neutral gas clusters for workpiece processing.

本發明的進一步目標為提供一種提供實質上無中尺度簇的高純度氣體簇束之設備及方法。 A further object of the present invention is to provide an apparatus and method for providing a high-purity gas cluster beam substantially free of mesoscale clusters.

本發明的更另一個目標為提供一種用以形成高純度、經聚焦的強中性原子或分子束之設備及方法,其中該束具有能量在約1電子伏特至多如幾千電子伏特的範圍內。 Still another object of the present invention is to provide an apparatus and method for forming a high-purity, focused, strong neutral atom or molecular beam, wherein the beam has an energy in the range of about 1 electron volt to as much as several thousand electron volts .

本發明的又另一個目標為與習知GCIBs比較,提供一種用以形成能改良表面平滑度的束之設備及方法。 Yet another object of the present invention is to provide an apparatus and method for forming beams with improved surface smoothness compared to conventional GCIBs.

本發明的目標為提供一種用以形成摻雜及/或變形的膜及/或用以將外來原子物種引進半導體或其它材料表面中的設備及方法,其中該經處理的表面與下面基材材料具有一界面,其係優於使用習知GCIB處理所形成的那些。 The object of the present invention is to provide an apparatus and method for forming a doped and/or deformed film and/or for introducing foreign atomic species into the surface of a semiconductor or other material, wherein the treated surface and the underlying substrate material Has an interface that is superior to those formed using conventional GCIB processing.

本發明的另一個目標為提供一種使用中性束在半導體或其它材料表面處形成非晶相區域之設備及方法, 及其中該與下面基材材料的界面係優於使用習知GCIB處理所形成者。 Another object of the present invention is to provide an apparatus and method for forming an amorphous phase region at the surface of a semiconductor or other material using a neutral beam, Among them, the interface with the underlying substrate material is better than that formed by the conventional GCIB process.

本發明的進一步目標為提供一種用以蝕刻表面的設備及方法,如與習知GCIB處理比較,其具有優異的最後平滑度。 A further object of the present invention is to provide an apparatus and method for etching a surface, which has an excellent final smoothness as compared with the conventional GCIB treatment.

本發明的又進一步目標為提供一種用以蝕刻光學表面的設備及方法,如與習知GCIB處理比較,其具有優異的最後平滑度。 A still further object of the present invention is to provide an apparatus and method for etching an optical surface, which has an excellent final smoothness as compared with the conventional GCIB treatment.

本發明的另一個目標為提供一種用以將一光學塗層黏附至一光學表面的設備及方法,其中該塗層具有的黏附力係優於藉由習知方法所獲得者。 Another object of the present invention is to provide an apparatus and method for adhering an optical coating to an optical surface, wherein the coating has an adhesion force superior to that obtained by conventional methods.

本發明的另一個目標為提供一種用以修改光學裝置表面以減低其對由於大氣曝露而降解之敏感性的方法,及提供因此改良的光學裝置。 Another object of the present invention is to provide a method for modifying the surface of an optical device to reduce its sensitivity to degradation due to atmospheric exposure, and to provide an improved optical device.

本發明的進一步目標為提供一種用以在吸濕性材料表面上形成阻礙物以減低該材料對吸收濕氣的敏感性之方法,及提供因此改良的材料。 A further object of the present invention is to provide a method for forming an obstacle on the surface of a hygroscopic material to reduce the sensitivity of the material to moisture absorption, and to provide a material thus improved.

本發明的更另一個目標為提供一種用以在半導體及/或其它材料表面上形成及/或生長膜的設備及方法,其中該膜與下面基材材料具有一界面,其係優於使用習知GCIB處理所形成的那些。 Still another object of the present invention is to provide an apparatus and method for forming and/or growing a film on the surface of semiconductors and/or other materials, wherein the film has an interface with the underlying substrate material, which is superior to the conventional Know those formed by GCIB processing.

本發明的額外目標為提供一種使用氣體簇及/或單體的中性束來處理電絕緣材料之設備及方法,其處理此等材料而沒有由束傳輸的電荷引發性損傷。 An additional object of the present invention is to provide an apparatus and method for processing electrically insulating materials using a neutral cluster of gas clusters and/or monomers, which processes these materials without charge-induced damage transmitted by the beam.

本發明的進一步目標為提供一種藉由中性束照射光學元件表面來改良該光學元件或寶石之性質的方法。 A further object of the present invention is to provide a method for improving the properties of an optical element or gemstone by irradiating the surface of the optical element with a neutral beam.

本發明的另一個目標為藉由中性束技術提供一種具有改良的性質之光學元件或寶石。 Another object of the present invention is to provide an optical element or gemstone with improved properties by neutral beam technology.

本發明的額外目標為提供一種在矽基材上形成SiC或SiCx層之方法。 An additional object of the present invention is to provide a method of forming a SiC or SiC x layer on a silicon substrate.

本發明的進一步目標為提供一種藉由中性束技術處理形成硬遮罩以進行無光阻微影蝕刻處理之方法,及提供因此製得的裝置。 A further object of the present invention is to provide a method for forming a hard mask by neutral beam technology to perform photoresist lithography etching treatment, and to provide a device thus produced.

發明概要 Summary of the invention

藉由於下列本文中所描述之本發明的多個具體實例達成上述提出的目標和本發明的進一步及其它目標及優點。 The above-mentioned objectives and further and other objectives and advantages of the invention are achieved by the following specific examples of the invention described herein.

在基材表面上形成圖案化的硬遮罩之無光阻方法包含一些步驟。藉由提供一減壓艙形成一加速的中性束;在該減壓艙內形成一包括包含碳原子之氣體簇離子之氣體簇離子束;在該減壓艙內加速該氣體簇離子以沿著一束路徑形成加速的氣體簇離子束;沿著該束路徑促進該加速的氣體簇離子之至少一部分碎裂及/或解離;在該減壓艙中從該束路徑移除帶電顆粒,以沿著該束路徑形成一加速的中性束。藉由將一圖案化樣板與該基材引進該減壓艙中來處理該基材;將該基材保持在該束路徑中;透過該圖案化樣板之開口,藉由該加速的中性束照射該基材之部分 表面來處理其,藉由將碳原子植入該表面的照射部分中,於該表面之照射部分上形成經硬化及/或緻密化的含碳圖案化層;分開該樣板與該基材;第一次蝕刻該具有含碳圖案化層之表面,以優先地移除該表面之不含碳部分的材料而形成一或多個溝槽及一或多個高原區;在該高原區及溝槽上形成一硬遮罩層;平坦化該硬遮罩層以從高原區移除其,但非從溝槽;及選擇性,使用該硬遮罩層作為遮罩第二次蝕刻該表面,以移除基材材料。 The photoresist-free method of forming a patterned hard mask on the surface of the substrate includes several steps. Forming an accelerated neutral beam by providing a decompression chamber; forming a gas cluster ion beam including gas cluster ions containing carbon atoms in the decompression chamber; accelerating the gas cluster ions in the decompression chamber to Forming a beam of accelerated gas cluster ions along a beam path; promoting fragmentation and/or dissociation of at least a portion of the accelerated gas cluster ions along the beam path; removing charged particles from the beam path in the decompression chamber to An accelerated neutral beam is formed along the beam path. Processing the substrate by introducing a patterned template and the substrate into the decompression chamber; holding the substrate in the beam path; through the opening of the patterned template, by the accelerated neutral beam Irradiate the substrate Surface to treat it, by implanting carbon atoms into the irradiated portion of the surface, forming a hardened and/or densified carbon-containing patterned layer on the irradiated portion of the surface; separating the template from the substrate; Etching the surface with the carbon-containing patterned layer at a time to preferentially remove the material of the surface that does not contain carbon to form one or more trenches and one or more plateau regions; in the plateau regions and trenches Forming a hard mask layer; planarizing the hard mask layer to remove it from the plateau area, but not from the trench; and optionally, using the hard mask layer as a mask to etch the surface a second time, to Remove the substrate material.

該移除步驟基本上可從該束路徑中移除全部帶電顆粒。該方法可在該移除步驟後進一步包括熱處理該基材之步驟。該中性束可基本上由來自該氣體簇離子束之氣體組成。該促進步驟可包括在該加速步驟中提高加速電壓,或在形成該氣體簇離子束時改良離子化效率。該促進步驟可包括增加在該加速的氣體簇離子束中之離子速度範圍。該促進步驟可包括將一或多種在形成該氣體簇離子束時所使用的氣體元素引進該減壓艙中以沿著該束路徑增加壓力。該促進步驟可包括以輻射能量照射該加速的氣體簇離子束或中性束。該處理工件的至少一部分表面之中性束可實質上由具有能量在1電子伏特至數千電子伏特間之單體組成。該處理步驟可進一步包括使用該加速的中性束掃描該基材以處理該表面之擴大部分。該基材可包含結晶或非晶矽。該處理步驟可形成SiCx(0.05<X<3)層。該硬遮罩層可包含二氧化矽。該第一次蝕刻步驟可使用一包含氬的第二加速中性束。該第二次蝕刻步驟可使用Cl2或CCl2F5電 漿蝕刻技術。該加速步驟可經由5至50千伏之電壓來加速該氣體簇離子。該方法處理步驟可植入碳原子至每平方公分1x1014至5x1016個離子的預定劑量。該含碳圖案化層可具有厚度約1至約3奈米。該第二次蝕刻步驟可留下該基材表面與該硬遮罩區域的底部共平面。 This removal step can remove substantially all charged particles from the beam path. The method may further include a step of heat treating the substrate after the removing step. The neutral beam may consist essentially of gas from the gas cluster ion beam. The promoting step may include increasing the accelerating voltage in the accelerating step, or improving the ionization efficiency when forming the gas cluster ion beam. The promoting step may include increasing the ion velocity range in the accelerated gas cluster ion beam. The promoting step may include introducing one or more gas elements used in forming the gas cluster ion beam into the decompression chamber to increase the pressure along the beam path. The promoting step may include irradiating the accelerated gas cluster ion beam or neutral beam with radiant energy. The neutral beam of at least a part of the surface of the treated workpiece may consist essentially of a monomer having an energy between 1 electron volt and thousands of electron volts. The processing step may further include scanning the substrate using the accelerated neutral beam to treat the enlarged portion of the surface. The substrate may include crystalline or amorphous silicon. This processing step can form a SiC x (0.05<X<3) layer. The hard mask layer may include silicon dioxide. This first etching step may use a second accelerated neutral beam containing argon. This second etching step may use Cl 2 or CCl 2 F 5 plasma etching technique. The acceleration step can accelerate the gas cluster ions through a voltage of 5 to 50 kV. The processing steps of the method can implant carbon atoms to a predetermined dose of 1x10 14 to 5x10 16 ions per square centimeter. The carbon-containing patterned layer may have a thickness of about 1 to about 3 nanometers. The second etching step can leave the substrate surface coplanar with the bottom of the hard mask area.

本發明的另一個具體實例在藉由上述步驟形成之基材表面上提供一圖案化的硬遮罩。 Another embodiment of the present invention provides a patterned hard mask on the surface of the substrate formed by the above steps.

本發明提供一種從加速的氣體簇離子束、加速的中性氣體簇及/或較佳為單體束取得之高束純度方法及系統,其可使用於多種型式的表面及淺次表面材料處理,及其對許多應用來說,能具有比習知GCIB處理優異的性能。其可提供經良好聚焦、加速的強中性單體束與具有能量在約1電子伏特至多如幾千電子伏特之範圍內的顆粒。在此能量範圍內,中性顆粒於許多應用中可有益或必需,例如,當想要打破表面或淺次表面鍵結以使得清潔、蝕刻、平滑化、沈積、非晶相化容易或產生表面化學效應時。在此情況中,每顆粒的能量約1電子伏特至最高幾千電子伏特可經常有用。對以簡單、相對不貴的設備來形成強中性束來說,此一能量範圍係不切實際。在多個具體實例中,該加速的中性束係使用於多種表面及淺次表面材料處理及藉由此處理方法製得提高的材料及裝置。 The present invention provides a high-beam purity method and system obtained from accelerated gas cluster ion beam, accelerated neutral gas cluster and/or preferably a single beam, which can be used for various types of surface and shallow subsurface material treatment , And for many applications, can have superior performance than conventional GCIB processing. It can provide well-focused, accelerated strong neutral monomer beams and particles with energies in the range of about 1 electron volt to as many as several thousand electron volts. Within this energy range, neutral particles can be beneficial or necessary in many applications, for example, when it is desired to break the surface or shallow subsurface bond to make cleaning, etching, smoothing, depositing, amorphous phase transformation easy or creating a surface Chemical effect. In this case, an energy per particle of about 1 electron volt to up to several thousand electron volts can often be useful. This energy range is impractical for forming strong neutral beams with simple and relatively inexpensive equipment. In various specific examples, the accelerated neutral beam system is used in the treatment of a variety of surface and shallow subsurface materials and the improved materials and devices made by this treatment method.

這些加速的中性束係藉由下列產生:首先形成習知加速的GCIB,然後藉由不會將雜質引進該束中之方法及操作條件來部分或基本上完全解離其,然後分離該束 之殘餘帶電部分與中性部分,隨後將所產生之加速的中性束使用於工件處理。依該氣體簇離子之解離程度而定,所產生的中性束可係中性氣體單體與氣體簇之混合物或可基本上全部或幾乎全部由中性氣體單體組成。最好該加速的中性束係一基本上完全解離的中性單體束。 These accelerated neutral beams are generated by first forming a conventionally accelerated GCIB, then partially or substantially completely dissociating them by methods and operating conditions that do not introduce impurities into the beam, and then separating the beam The residual charged part and the neutral part are then used to process the accelerated neutral beam. Depending on the degree of dissociation of the gas cluster ions, the generated neutral beam may be a mixture of neutral gas monomers and gas clusters or may consist essentially or almost entirely of neutral gas monomers. Preferably, the accelerated neutral beam is a neutral monomer beam that is substantially completely dissociated.

可由本發明的具體實例之方法及設備產生的中性束之優點為,它們可使用來處理電絕緣材料而沒有如包括GCIB的全部離子化束通常發生般,由於此等材料之表面因束傳輸的電荷帶電而對該材料產生損傷。例如,在半導體及其它電子應用中,離子經常促成薄介電膜諸如氧化物、氮化物等等損傷或破壞性帶電。使用中性束可成功地束處理聚合物、介電質及/或在離子束可由於表面帶電或其它帶電效應而產生無法接受的副作用之其它電絕緣或高電阻率材料、塗佈物及膜的其它應用中。實施例包括(非為限制)腐蝕抑制性塗佈物之處理、及有機膜之照射交聯及/或聚合。在其它實施例中,中性束引發的聚合物或其它介電材料之改質(例如,殺菌、平滑化、改良表面生物配伍、及改良藥物的附著性及/或控制其溶析速率)可讓此等材料能夠使用在醫療裝置中用於植入及/或其它醫療/外科應用。進一步實施例包括玻璃、聚合物及陶瓷活體培養(bio-culture)實驗室器皿及/或環境採樣表面之中性束處理,其中此束可使用來改良表面特徵,如例如,粗糙度、平滑度、親水性及生物配伍。 The advantages of neutral beams that can be generated by the methods and apparatus of specific examples of the present invention are that they can be used to process electrically insulating materials without the usual occurrence of all ionized beams including GCIB, due to the beam transmission on the surface of these materials The electric charge is charged and damages the material. For example, in semiconductor and other electronic applications, ions often contribute to the damage or destructive charging of thin dielectric films such as oxides, nitrides, etc. Neutral beams can be used to successfully treat polymers, dielectrics, and/or other electrically insulating or high-resistivity materials, coatings, and films that can cause unacceptable side effects due to surface charging or other charging effects. In other applications. Examples include, but are not limited to, treatment of corrosion-inhibiting coatings, and irradiation crosslinking and/or polymerization of organic films. In other embodiments, the modification of neutral beam-induced polymers or other dielectric materials (eg, sterilization, smoothing, improved surface biocompatibility, and improved drug adhesion and/or control of its dissolution rate) may These materials can be used in medical devices for implantation and/or other medical/surgical applications. Further examples include glass, polymer, and ceramic bio-culture laboratory vessels and/or environmental sampling surface neutral beam treatment, where this beam can be used to improve surface characteristics such as, for example, roughness, smoothness , Hydrophilicity and biological compatibility.

因為可藉由本發明的具體實例之方法及設備從 其形成加速的中性束之母GCIB包含離子,其容易加速至想要的能量及容易使用習知的離子束技術聚焦。在隨後的解離及分離帶電離子與中性顆粒後,該中性束顆粒趨向於保留其經聚焦的軌跡及可以好的效應傳輸廣闊的距離。 Because the method and equipment of the specific examples of the present invention can be used The mother GCIB, which forms an accelerated neutral beam, contains ions, which are easily accelerated to the desired energy and are easily focused using conventional ion beam techniques. After the subsequent dissociation and separation of charged ions and neutral particles, the neutral beam particles tend to retain their focused trajectory and can transmit a wide distance with good effects.

當在噴射器中的中性氣體簇藉由電子轟炸而離子化時,它們變熱及/或經激發。此可造成單體在加速後,當其沿著束線行進時,隨後從該離子氣體簇中蒸發。額外的是,該氣體簇離子與背景氣體分子在電離器、加速器及束線區域中碰撞亦加熱及激發該氣體簇離子,及可額外造成在加速後隨後從該氣體簇離子中放出單體。當這些用以放出單體的機制係由電子轟炸及/或與形成GCIB相同的氣體之背景氣體分子(及/或其它氣體簇)碰撞而引發時,該束並無由該造成釋放出單體的解離製程所促成之污染物。 When the neutral gas clusters in the ejector are ionized by electron bombardment, they become hot and/or excited. This can cause the monomer to accelerate after it accelerates and then evaporates from the ion gas cluster as it travels along the beam line. Additionally, the collision of the gas cluster ions with background gas molecules in the ionizer, accelerator, and beamline regions also heats and excites the gas cluster ions, and can additionally cause monomer to be subsequently released from the gas cluster ions after acceleration. When these mechanisms for releasing monomers are triggered by electron bombardment and/or collision with background gas molecules (and/or other gas clusters) that form the same gas as GCIB, the beam does not release monomers by this Pollutants caused by the dissociation process.

可使用其它機制來解離在GCIB中的氣體簇離子(或引發從其放出單體)而沒有將污染物引進該束中。亦可使用這些機制之某些來解離在中性氣體簇束中的中性氣體簇。機制之一為使用紅外線或其它雷射能量進行雷射照射該簇離子束。在經雷射照射的GCIB中,該氣體簇離子之雷射引發的加熱造成該氣體簇離子之激發及/或加熱及造成隨後從該束中放出單體。另一種機制為讓該束通過熱加熱管,以便輻射熱能量光子衝擊在束中的氣體簇離子。由在該管中的輻射熱能引發的加熱該氣體簇離子造成該氣體簇離子之激發及/或加熱及造成隨後從該束中放出單體。 在另一種機制中,該氣體簇離子束與與在形成GCIB時所使用的來源氣體(或其它非污染氣體)相同之氣體或混合物的噴射氣體交叉,造成在該噴射氣體中的氣體單體與在該離子束中之氣體簇碰撞,此產生激發及/或加熱在該束中的氣體簇離子及隨後從該經激發的氣體簇離子中放出單體。藉由完全與在電子轟炸的初始離子化期間、及/或於該束內碰撞(與其它簇離子,或與那些使用來形成GCIB相同的氣體之背景氣體分子)、及/或雷射或熱輻射、及/或與非污染氣體交叉噴射碰撞來產生該GCIB解離及/或碎裂相依,避免該束因與其它材料碰撞而污染。 Other mechanisms can be used to dissociate the gas cluster ions in GCIB (or trigger the release of monomers therefrom) without introducing contaminants into the beam. It is also possible to use some of these mechanisms to dissociate the neutral gas clusters in the neutral gas cluster beam. One of the mechanisms is to use infrared or other laser energy for laser irradiation of the cluster ion beam. In a laser-irradiated GCIB, the laser-induced heating of the gas cluster ions causes excitation and/or heating of the gas cluster ions and subsequent release of monomer from the beam. Another mechanism is to pass the beam through a heat-heated tube so that radiant thermal energy photons impact the gas cluster ions in the beam. The heating of the gas cluster ions initiated by the radiant heat energy in the tube causes the excitation and/or heating of the gas cluster ions and causes the subsequent release of monomer from the beam. In another mechanism, the gas cluster ion beam crosses the jet gas of the same gas or mixture as the source gas (or other non-polluting gas) used in the formation of GCIB, causing the gas monomer in the jet gas to The gas clusters in the ion beam collide, which generates excited and/or heated gas cluster ions in the beam and then releases monomers from the excited gas cluster ions. By completely colliding with the initial ionization of the electron bombardment, and/or within the beam (with other cluster ions, or with background gas molecules used to form the same gas as GCIB), and/or laser or heat Radiation, and/or cross-spray collision with non-polluting gas to generate the GCIB dissociation and/or fragmentation dependence, to avoid contamination of the beam due to collision with other materials.

透過使用上述的此不污染解離方法,該GCIB解離或至少部分解離而沒有將不為原始來源氣體原子的部分之原子引進該解離產物或殘餘簇。藉由使用用以形成初始簇的來源氣體來避免該工件之污染,其中該來源氣體不包括對欲使用該殘餘簇或解離產物進行處理的工件將係污染物的原子。當使用氬或其它惰性氣體時,該來源氣體材料具揮發性及不具化學反應性,及在隨後使用該中性束照射工件後,從該工件完全釋放出這些揮發性無反應性原子。因此,對包括玻璃、石英、藍寶石、鑽石及其它硬的透明材料諸如三硼酸鋰(LBO)之光學及寶石材料的工件來說,氬及其它惰性氣體可提供作為來源氣體材料而對由於中性束照射之污染沒有貢獻。在其它情況中,可使用其它來源氣體,其限制為該來源氣體構成原子不包括將造成該工件污染之原子。例如,對某些玻璃工件來說,LBO及多種其 它光學材料係包含氧,故氧原子不會提供作為污染物。在此情況中,可使用含氧來源氣體而沒有污染物。 By using this non-contaminating dissociation method described above, the GCIB dissociates or at least partially dissociates without introducing atoms that are not part of the original source gas atoms into the dissociation product or residual cluster. The contamination of the workpiece is avoided by using the source gas used to form the initial cluster, where the source gas does not include atoms that will be contaminants for the workpiece to be processed using the residual cluster or dissociation product. When argon or other inert gas is used, the source gas material is volatile and not chemically reactive, and after the workpiece is subsequently irradiated with the neutral beam, the volatile non-reactive atoms are completely released from the workpiece. Therefore, for optical and gem materials including glass, quartz, sapphire, diamond, and other hard transparent materials such as lithium triborate (LBO), argon and other inert gases can be provided as source gas materials and are The pollution of beam irradiation does not contribute. In other cases, other source gases may be used, with the limitation that the source gas constituent atoms do not include atoms that will cause contamination of the workpiece. For example, for some glass workpieces, LBO and many other Its optical material system contains oxygen, so oxygen atoms will not be provided as pollutants. In this case, oxygen-containing source gas can be used without pollutants.

當從噴嘴噴射出的中性氣體簇行進通過電子經定向以離子化該簇之離子化區域時,該簇可保持未離子化或可獲得一或多個電荷(藉由入射的電子從該簇噴出電子)之電荷狀態q。該電離器操作條件影響氣體簇將取得的特別電荷狀態之可能性,其中更強的電離器條件將產生較大機率達成較高的電荷狀態。產生較高離子化效率之更強的電離器條件可產生自較高的電子通量及/或較高(在極限內)的電子能量。一旦該氣體簇已經離子化,典型會將其從電離器中引出,聚焦成束及藉由落入電場而加速。該氣體簇離子的加速量容易地藉由控制該加速電場之大小而控制。典型的商業GCIB處理工具通常提供該欲藉由電場加速之氣體簇離子,其中該電場具有可調整的加速電壓VAcc,其典型為例如約1千伏至70千伏(但不限於該範圍,VAcc最高200千伏或甚至更高係可行)。因此,在1至70千電子伏特內的能量範圍達成單一帶電氣體簇離子(或更高,若使用較大的VAcc時),及在3至210千電子伏特內之能量範圍達成多重帶電(例如但非為限制電荷狀態q=3電子電荷)氣體簇離子(或更高,對較高的VAcc來說)。對其它氣體簇離子電荷狀態及加速電壓來說,每簇的加速能量係qVAcc電子伏特。來自具有所提供的離子化效率之所提供的電離器,氣體簇離子將具有從零(未離子化)至較高數目諸如例如6(或具有高電離器效率,甚至更高)之電荷狀態分佈,及該電荷狀態分佈 的最可能及平均值亦隨著電離器效率增加(較高的電子通量及/或能量)而增加。較高的電離器效率亦造成在電離器中形成的氣體簇離子數目增加。在許多情況中,當在高效率下操作該電離器而造成GCIB電流增加時,GCIB處理生產量增加。此操作的不利處為可在中尺度氣體簇離子上發生多重帶電狀態,可由那些離子增加坑洞及/或形成粗糙界面,而此效應經常會對該處理的意圖產生反效果地操作。因此,對許多GCIB表面處理配方來說,電離器操作參數之選擇趨向於包括更多考慮而非僅最大化束電流。在某些方法中,可使用”壓力單元”(參見美國專利7,060,989,Swenson等人),藉由調整該束能量,藉由在提昇壓力的”壓力單元”中進行氣體碰撞准許於高離子化效率下操作電離器,同時仍然獲得可接受的束處理性能。 When a neutral gas cluster ejected from the nozzle travels through an ionized region where electrons are oriented to ionize the cluster, the cluster can remain unionized or one or more charges can be obtained (by incident electrons from the cluster The state of charge q of the ejected electrons). The ionizer operating conditions affect the possibility of a particular charge state that the gas cluster will achieve, where stronger ionizer conditions will produce a greater chance of achieving a higher charge state. Stronger ionizer conditions that produce higher ionization efficiency can result from higher electron flux and/or higher (within limits) electron energy. Once the gas cluster has been ionized, it is typically taken out of the ionizer, focused into a beam and accelerated by falling into an electric field. The acceleration amount of the gas cluster ion is easily controlled by controlling the magnitude of the acceleration electric field. A typical commercial GCIB processing tool usually provides the gas cluster ions to be accelerated by an electric field, where the electric field has an adjustable acceleration voltage V Acc , which is typically, for example, about 1 kV to 70 kV (but not limited to this range, V Acc up to 200 kV or even higher is feasible). Therefore, a single charged gas cluster ion (or higher, if a larger V Acc is used) is achieved in the energy range of 1 to 70 kiloelectron volts, and multiple charges are achieved in the energy range of 3 to 210 kiloelectron volts ( For example, but not to limit the charge state q=3 electron charge) gas cluster ions (or higher, for higher V Acc ). For other gas cluster ion charge states and acceleration voltages, the acceleration energy of each cluster is qV Acc electron volts. From the provided ionizer with the provided ionization efficiency, the gas cluster ions will have a charge state distribution from zero (not ionized) to a higher number such as, for example, 6 (or with high ionizer efficiency, or even higher) , And the most likely and average value of the charge state distribution also increases as the ionizer efficiency increases (higher electron flux and/or energy). The higher ionizer efficiency also causes an increase in the number of gas cluster ions formed in the ionizer. In many cases, when operating the ionizer at high efficiency resulting in an increase in GCIB current, the throughput of the GCIB process increases. The disadvantage of this operation is that multiple charged states can occur on the medium-scale gas cluster ions, and pits can be added and/or rough interfaces can be formed by those ions, and this effect often operates counter to the intention of the treatment. Therefore, for many GCIB surface treatment formulations, the choice of ionizer operating parameters tends to include more considerations than just maximizing the beam current. In some methods, a "pressure unit" (see US Patent 7,060,989, Swenson et al.) can be used, and by adjusting the beam energy, high ionization efficiency is permitted by performing gas collisions in a "pressure unit" that raises pressure Operate the ionizer while still achieving acceptable beam handling performance.

當在本發明的具體實例中形成中性束時,於高效率下操作該電離器並無不利,事實上此操作有時較佳。當該電離器係在高效率下操作時,在由該電離器產生之氣體簇離子中可有廣泛的電荷狀態範圍。此在該電離器與加速電極間的引出區域中及亦在該下游束中產生廣泛速度範圍的氣體簇離子。此可造成在束中之氣體簇離子間及當中的碰撞頻率提高,此通常造成最大氣體簇離子的較高碎裂程度。此碎裂可造成在該束中的簇尺度重新分配,讓其朝向較小簇尺度偏移。這些簇碎片保留的能量與其新尺度(N)成比例,如此變成較少高能量,同時基本上保留該初始未破碎經加速的氣體簇離子之速度。已經實驗證實在碰撞後 之能量變化與速度保留(如例如在Toyoda,N.等人,”Cluster size dependence on energy and velocity distributions of gas cluster ions after collisions with residual gas”,Nucl.Instr.& Meth.in Phys.Research B 257(2007),pp 662-665中報導)。碎裂亦可造成在簇碎片中的電荷重新分配。類似地產生之某些未帶電的碎片及多電荷氣體簇離子可破碎成數個帶電氣體簇離子及或許某些未帶電碎片。要由發明家了解的是,在電離器及引出區域中的聚焦場之設計可提高較小氣體簇離子及單體離子的聚焦以增加在束引出區域中及在下游束中與較大氣體簇離子碰撞的可能性,因此促成該氣體簇離子解離及/或破碎。 When a neutral beam is formed in a specific example of the present invention, it is not disadvantageous to operate the ionizer at high efficiency, in fact, this operation is sometimes preferable. When the ionizer is operated at high efficiency, there can be a wide range of charge states in the gas cluster ions generated by the ionizer. This generates gas cluster ions in a wide velocity range in the extraction region between the ionizer and the acceleration electrode and also in the downstream beam. This can result in increased collision frequency between and among the gas cluster ions in the beam, which usually results in a higher degree of fragmentation of the largest gas cluster ions. This fragmentation can cause cluster size redistribution in the beam, shifting it towards smaller cluster sizes. The energy retained by these cluster fragments is proportional to its new scale (N), thus becoming less high energy, while substantially retaining the velocity of the initially unbroken accelerated gas cluster ions. It has been experimentally confirmed that after the collision Energy change and speed retention (such as in Toyoda, N. et al., "Cluster size dependence on energy and velocity distributions of gas cluster ions after collisions with residual gas", Nucl.Instr.& Meth.in Phys.Research B 257 (2007), reported in pp 662-665). Fragmentation can also cause redistribution of charge in cluster fragments. Some uncharged fragments and multi-charged gas cluster ions generated similarly can be broken into several charged gas cluster ions and perhaps some uncharged fragments. It should be understood by the inventors that the design of the focusing field in the ionizer and the extraction area can improve the focusing of the smaller gas cluster ions and monomer ions to increase the larger gas clusters in the beam extraction area and in the downstream beam The possibility of ion collision, thus contributing to the dissociation and/or fragmentation of the gas cluster ions.

在本發明的具體實例中,可選擇性安排於電離器、加速區域及束線中的背景氣體壓力,以便其具有比正常使用於好的GCIB傳送還要高之壓力。此可造成額外從該氣體簇離子中放出單體(除了產生自加熱及/或產生自初始氣體簇離子化事件的激發外)。該壓力可經安排,以便該氣體簇離子在該電離器與工件間具有足夠短的平均自由徑及足夠長的飛行路徑,在該路徑中它們必需與背景氣體分子進行多重碰撞。 In a specific example of the present invention, the background gas pressure in the ionizer, acceleration region, and beam line can be selectively arranged so that it has a higher pressure than the GCIB transmission normally used for good. This can cause additional monomer to be released from the gas cluster ions (in addition to self-heating and/or excitation from the initial gas cluster ionization event). The pressure can be arranged so that the gas cluster ions have a sufficiently short average free path and a sufficiently long flight path between the ionizer and the workpiece, where they must make multiple collisions with background gas molecules.

對包括N個單體及具有q電荷狀態且已經透過VAcc伏特的電場電壓降加速之均質氣體簇離子來說,該簇將具有每單體大約qVAcc/NI電子伏特的能量,其中NI為在加速那時於該簇離子中之單體數目。除了最小的氣體簇離子外,此離子與和該簇來源氣體相同氣體之背景氣體單體 碰撞將造成額外大約qVAcc/NI電子伏特堆積進該氣體簇離子中。與整體氣體簇離子能量(qVAcc)比較,此能量相對小及通常造成該簇之激發或加熱及隨後從該簇中放出單體。咸信此較大簇與背景氣體之碰撞很少碎裂該簇,而是加熱及/或激發其以造成藉由蒸發或類似機制放出單體。不管造成從氣體簇離子中放出單體的激發來源,所釋放出之單體具有每顆粒大約相同的能量qVAcc/NI電子伏特,及保留與釋放出其之氣體簇離子大約相同的速度及軌道。當發生從氣體簇離子中放出此單體時,不論它們是產生自由於原始離子化事件、碰撞或輻射加熱的激發或加熱,有高機率保留該電荷與較大的殘餘氣體簇離子。因此,在一連串的單體放出後,大的氣體簇離子可還原成共行進的單體與或許較小的殘餘氣體簇離子(或可能數種,若亦已發生碎裂時)雲。遵循原始束軌道共行進的單體全部具有與原始氣體簇離子大約相同的速度,及各者具有大約qVAcc/NI電子伏特的能量。對小的氣體簇離子來說,與背景氣體單體碰撞的能量可能完全及激烈地解離該小的氣體簇,及不確定在此情況中所產生的單體是持續與該束行進或從該束噴出。 For a homogeneous gas cluster ion that includes N monomers and has a state of charge of q and has been accelerated by an electric field voltage drop of V Acc volts, the cluster will have an energy of approximately qV Acc /NI electron volts per monomer, where NI is The number of monomers in the cluster ion at the time of acceleration. Except for the smallest gas cluster ion, collision of this ion with the background gas monomer of the same gas as the cluster source gas will cause an additional approximately qV Acc /NI electron volts to accumulate into the gas cluster ion. Compared to the overall gas cluster ion energy (qV Acc ), this energy is relatively small and usually causes excitation or heating of the cluster and subsequent release of monomer from the cluster. It is believed that the collision of this larger cluster with the background gas rarely breaks the cluster, but heats and/or excites it to cause the monomer to be released by evaporation or a similar mechanism. Regardless of the excitation source that causes the monomer to be released from the gas cluster ions, the released monomer has approximately the same energy per particle qV Acc /NI electron volts, and retains approximately the same velocity and orbit as the gas cluster ions that release it . When this monomer is released from the gas cluster ions, whether they are excited or heated from the original ionization event, collision or radiant heating, there is a high probability of retaining this charge and larger residual gas cluster ions. Therefore, after a series of monomers are released, large gas cluster ions can be reduced to a cloud of co-propagating monomers and perhaps smaller residual gas cluster ions (or possibly several, if fragmentation has also occurred). All the monomers that follow the original beam orbit all have approximately the same velocity as the original gas cluster ions, and each has an energy of approximately qV Acc /NI electron volts. For small gas cluster ions, the energy of collision with the background gas monomer may dissociate the small gas cluster completely and violently, and it is uncertain whether the monomer produced in this case continues to travel with or from the beam The beam squirted out.

為了避免該束因為與背景氣體碰撞受污染,最好該背景氣體係與構成該氣體簇離子的氣體相同之氣體。用以形成噴射氣體簇的噴嘴典型以級數100-600sccm的高氣體流進行操作。此流之未壓縮進氣體簇中的部分提高在該來源艙中的壓力。除了以氣體簇形式傳送通過該漏杓孔 的氣體外,來自該來源艙之未團簇化的來源氣體可流過該漏杓孔至下游束線或束路徑艙。對該漏杓孔的直徑進行選擇以便從該來源艙至束線提供一增加的未團簇之來源氣體流,此係一種方便提供增加的束線壓力以引發背景氣體與GCIB碰撞之方法。因為該高來源氣體流(通過該漏杓孔之未團簇的氣體及由該束傳輸至標靶的氣體),從該束線快速充入常壓氣體。此外,氣體可漏進該束線艙中,或如上述指出般,以與GCIB路徑交叉的噴射物引進。在此情況中,該氣體較佳為與來源氣體相同(或惰性或其它方面非污染物)。在關鍵性應用中,當背景氣體碰撞在單體放出中扮演一定角色時,可在該束線中使用殘餘氣體分析器以確認背景氣體的品質。 In order to prevent the beam from being contaminated by collision with the background gas, it is preferable that the background gas system is the same gas as the gas constituting the gas cluster ion. The nozzles used to form jet gas clusters are typically operated with a high gas flow in the order of 100-600 sccm. The portion of this stream that is not compressed into the gas cluster increases the pressure in the source chamber. In addition to passing through the skimmer hole as a gas cluster In addition to the gas, the unclustered source gas from the source compartment can flow through the skimmer hole to the downstream beam line or beam path compartment. The diameter of the skimmer hole is selected to provide an increased flow of unclustered source gas from the source chamber to the beamline. This is a convenient method to provide increased beamline pressure to trigger the collision of background gas and GCIB. Because of the high-source gas flow (unclustered gas passing through the dipper hole and gas transported from the beam to the target), atmospheric gas is quickly filled from the beam line. In addition, gas can leak into the beam compartment or, as indicated above, be introduced as a jet that crosses the GCIB path. In this case, the gas is preferably the same as the source gas (or inert or otherwise non-polluting). In critical applications, when background gas collisions play a role in the release of monomers, a residual gas analyzer can be used in the beam line to confirm the quality of the background gas.

在GCIB到達工件前,分離於該束中的殘餘帶電顆粒(氣體簇離子,特別是小及中尺度氣體簇離子及某些帶電單體,但是亦包括任何殘餘的大氣體簇離子)與該束之中性部分,僅留下中性束來處理該工件。 Before the GCIB reaches the workpiece, the residual charged particles (gas cluster ions, especially small and mesoscale gas cluster ions and some charged monomers, but also any residual large gas cluster ions) separated from the beam and the beam In the neutral part, only the neutral beam is left to process the workpiece.

於典型操作中,在該處理標靶處,該中性束的功率相對於所傳輸之完整(帶電加上中性)束的功率之分量係在約5%至95%的範圍內,如此藉由於本文中所揭示出的分離方法及設備,可由中性束將該完全加速的帶電束之部分動能傳輸至標靶。 In typical operation, at the processing target, the component of the power of the neutral beam relative to the power of the complete (charged plus neutral) beam transmitted is in the range of about 5% to 95%. Due to the separation method and equipment disclosed herein, a part of the kinetic energy of the fully accelerated charged beam can be transmitted to the target by a neutral beam.

藉由下列方式促進該氣體簇離子解離及因此產生高中性單體束能量:1)在較高加速電壓下操作。此對任何所提供的簇尺度 增加qVAcc/N;2)在高電離器效率下操作。此藉由增加q對任何所提供的簇尺度增加qVAcc/N,及由於在簇間之電荷狀態差異而於引出區域中在簇-離子碰撞上增加簇離子;3)在高電離器、加速區域或束線壓力下操作,或使用噴射氣體與該束交叉操作,或使用較長的束路徑,此全部增加背景氣體與任何所提供的氣體簇離子尺度碰撞之機率;4)使用雷射照射或熱輻射加熱該束進行操作,此直接促進從該氣體簇離子中放出單體;及5)在較高的噴嘴氣流下操作,此增加團簇及或許未團簇的氣體傳輸進該GCIB軌道中,此增加碰撞產生較大的單體放出。 The dissociation of the gas cluster ions and therefore the generation of highly neutral monomer beam energy is promoted by: 1) operating at a higher acceleration voltage. This increases qV Acc /N for any cluster size provided; 2) Operates at high ionizer efficiency. This increases qV Acc /N by increasing q to any provided cluster size, and increases cluster ions on cluster-ion collisions in the extraction region due to the difference in charge state between clusters; 3) In high ionizers, acceleration Operating under regional or beamline pressure, or using jet gas to cross the beam, or using a longer beam path, this all increases the probability of background gas colliding with any provided gas cluster ion scale; 4) using laser irradiation Or thermal radiation heating the beam for operation, which directly promotes the release of monomer from the gas cluster ions; and 5) operation under a higher nozzle gas flow, which increases the transmission of clustered and perhaps unclustered gas into the GCIB orbit In the middle, this increased collision produces larger monomer emissions.

為了產生背景氣體碰撞,從引出區域至工件的氣體簇離子束路徑長度乘以在該區域中之壓力的乘積有助於該氣體簇離子發生的解離程度。對30千伏加速來說,提供平均氣體簇離子電荷狀態1或較大及壓力乘以束路徑長度係6x10-3托耳-公分(0.8帕斯卡-公分)(在25℃下)之電離器參數提供一基本上完全解離成中性高能量單體的中性束(在與殘餘帶電離子分離後)。方便及習慣上標出壓力乘以束路徑長度的特徵作為氣體標靶厚度。6x10-3托耳-公分(0.8帕斯卡-公分)與大約1.94x1014氣體分子/平方公分的氣體標靶厚度相應。在一個範例性(非為限制)具體實例中,該背景氣體壓力係6x10-5托耳(8x10-3帕斯卡)及該束路徑長度係100公分,該加速電壓係30千伏,及於此情況中,已觀察到該中性束在該束路徑的末端處基本上完全解離成單體。此係沒有雷射或輻射束加熱及沒有使用與該束交叉的 噴射氣體。該完全解離之經加速的中性束狀態產生自由於該簇離子化事件、與殘餘氣體單體碰撞、及在束中之簇間碰撞的簇加熱之單體放出。 In order to produce background gas collisions, the product of the path length of the gas cluster ion beam from the extraction area to the workpiece times the pressure in this area contributes to the degree of dissociation of the gas cluster ions. For 30 kV acceleration, provide ionizer parameters with an average gas cluster ion charge state of 1 or greater and the pressure multiplied by the beam path length of 6x10 -3 Torr-cm (0.8 Pascal-cm) (at 25°C) Provide a neutral beam that is substantially completely dissociated into neutral high-energy monomers (after separation from residual charged ions). It is convenient and customary to mark the pressure multiplied by the beam path length as the gas target thickness. 6x10 -3 Torr-cm (0.8 Pascal-cm) corresponds to a gas target thickness of approximately 1.94x10 14 gas molecules per square centimeter. In an exemplary (non-limiting) specific example, the background gas pressure is 6x10 -5 Torr (8x10 -3 Pascal) and the beam path length is 100 cm, the acceleration voltage is 30 kV, and in this case In, it has been observed that the neutral beam is substantially completely dissociated into monomers at the end of the beam path. This system has no laser or radiation beam heating and does not use jet gas that crosses the beam. The fully dissociated accelerated neutral beam state results in the release of monomer heated by the cluster ionization event, collision with residual gas monomers, and collision between clusters in the beam.

與完整的束比較,使用該解離的中性束在平滑化黃金膜上產生改良的平滑化結果。在另一個應用中,將該解離的中性束使用在醫療裝置之藥物表面塗層上、或在醫療裝置之藥物-聚合物-混合物層上、或在醫療裝置的藥物-聚-混合物主體上,此提供改良的藥物附著性及修改藥物溶析速率而沒有當使用完整的GCIB時所發生之藥物重量損失。 Compared with the complete beam, the use of this dissociated neutral beam produces improved smoothing results on the smoothed gold film. In another application, the dissociated neutral beam is used on the drug surface coating of the medical device, or on the drug-polymer-mixture layer of the medical device, or on the drug-poly-mixture body of the medical device This provides improved drug adhesion and modified drug leaching rates without the weight loss of drugs that occurs when using full GCIB.

無法如方便用於氣體簇離子束般藉由電流測量對該中性束進行測量。當以中性束照射工件時,使用中性束功率感應器來幫助劑量測定。該中性束感應器係一種截取該束(或選擇性已知的束樣品)之熱感應器。該感應器的溫度提高速率係與產生自該感應器之高能量束照射的能量通量相關。必需在該感應器之有限的溫度範圍內進行該熱測量以避免由於入射在該感應器上的能量之熱再輻射產生誤差。對GCIB方法來說,該束功率(瓦)係等於束電流(安培)乘以束加速電壓VAcc。當GCIB照射工件一段時間(秒)時,由該工件所接收的能量(焦耳)係該束功率與該照射時間的乘積。當使用此束來處理一擴大的面積時,其處理效應係分佈在該面積(例如,平方公分)內。對離子束來說,習知上已經合宜地就照射的離子/平方公分來具體指定該處理劑量,其中該離子係已知或假設在加速那時具有平均 電荷狀態q,及已經透過電壓差VAcc伏特加速,以便每個離子攜帶qVAcc電子伏特(一電子伏特係大約1.6x10-19焦耳)的能量。因此,具有平均電荷狀態q、藉由VAcc加速及以離子/平方公分具體指出的離子束劑量與容易計算之以焦耳/平方公分表示的能量劑量相應。對來自加速的GCIB、如在本發明的具體實例中所使用之加速的中性束來說,在加速那時的q值及VAcc值對該束之帶電與未帶電分量二者(晚後形成及分離)係相同。GCIB的二種(中性及帶電)分量之功率係與在每個束分量中的質量呈比例進行劃分。因此,對如在本發明的具體實例中所使用之加速的中性束來說,當照射相等面積一段相等時間時,由該中性束所堆積的能量劑量(焦耳/平方公分)必需少於由完整的GCIB所堆積之能量劑量。藉由使用熱感應器來測量在完整的GCIB中之功率PG及在中性束中的功率PN(通常發現其係完整的GCIB之約5%至約95%),可計算出一使用在中性束處理劑量測定法中之補償因子。當PN係等於aPG時,則該補償因子係k=1/a。因此,若使用來自GCIB的中性束處理工件,而其達成劑量D離子/平方公分之時間週期係大於完整的GCIB(包括帶電及中性束部分)所需要之處理週期的k倍時,則由該中性束及完整的GCIB二者堆積在該工件中之能量劑量係相同(雖然結果可由於在處理效應中之性質差異,由於在二個束中的顆粒尺度差異而不同)。如於本文中所使用,以此方式補償之中性束處理劑量有時描述為具有與劑量D離子/平方公分等值的能量/平方公分。 The neutral beam cannot be measured by current measurement as convenient for the gas cluster ion beam. When irradiating the workpiece with a neutral beam, a neutral beam power sensor is used to aid dosimetry. The neutral beam sensor is a thermal sensor that intercepts the beam (or a beam sample of known selectivity). The rate of temperature increase of the sensor is related to the energy flux irradiated by the high energy beam generated from the sensor. The thermal measurement must be performed within the limited temperature range of the sensor to avoid errors due to thermal re-radiation of energy incident on the sensor. For the GCIB method, the beam power (watts) is equal to the beam current (amperes) times the beam acceleration voltage V Acc . When GCIB irradiates a workpiece for a period of time (seconds), the energy (joules) received by the workpiece is the product of the beam power and the irradiation time. When this beam is used to treat an enlarged area, its processing effect is distributed within that area (eg, square centimeters). For ion beams, it has been conventionally appropriate to specify the treatment dose in terms of ions/cm2 irradiated, where the ion is known or assumed to have an average state of charge q at the time of acceleration, and the voltage difference V has been transmitted Acc volts are accelerated so that each ion carries the energy of qV Acc electron volts (one electron volt is about 1.6x10 -19 Joules). Therefore, the ion beam dose with the average charge state q, acceleration by V Acc and specified in ions per square centimeter corresponds to the energy dose in joules per square centimeter that is easy to calculate. For a GCIB from acceleration, an accelerated neutral beam as used in a specific example of the invention, the q value and V Acc value at the time of acceleration are both charged and uncharged components of the beam (later Formation and separation are the same. The power of the two (neutral and charged) components of GCIB is divided in proportion to the mass in each beam component. Therefore, for an accelerated neutral beam as used in a specific example of the present invention, when the same area is irradiated for an equal period of time, the energy dose (Joules/cm2) accumulated by the neutral beam must be less than The energy dose accumulated by the complete GCIB. By using a thermal sensor to measure the power PG in the complete GCIB and the power PN in the neutral beam (it is usually found to be about 5% to about 95% of the complete GCIB), one can calculate Compensation factor in sex beam treatment dosimetry. When the PN system is equal to aPG, the compensation factor system k=1/a. Therefore, if a neutral beam from GCIB is used to process the workpiece, and the time period to reach the dose D ion/cm 2 is greater than k times the processing period required for a complete GCIB (including charged and neutral beam parts), then The energy dose deposited in the workpiece by both the neutral beam and the complete GCIB is the same (although the results may vary due to the difference in properties in the processing effect and due to the difference in particle size in the two beams). As used herein, compensating the neutral beam treatment dose in this way is sometimes described as having an energy per square centimeter equal to the dose D ions per square centimeter.

在許多情況中,使用來自氣體簇離子束之中性束與用於劑量測定的熱功率感應器組合,與使用完整的氣體簇離子束或經截取或經轉移的部分比較具有優點,其中該離子束不可避免地包含氣體簇離子及中性氣體簇及/或中性單體之混合物,及為了劑量測定目的,其習知上係使用束電流測量來度量。某些優點係如下: In many cases, using a neutral beam from a gas cluster ion beam in combination with a thermal power sensor for dosimetry has advantages over using a complete gas cluster ion beam or an intercepted or transferred portion, where the ion The beam inevitably contains a mixture of gas cluster ions and neutral gas clusters and/or neutral monomers, and for dosimetry purposes it is conventionally measured using beam current measurements. Some advantages are as follows:

1)該中性束伴隨著使用熱感應器來劑量測定可讓該劑量測定法更精確,因為其測量該束的總功率。若使用傳統的束電流測量對GCIB進行劑量測定時,該劑量測定法僅會測量及使用到該束之離子化部分的貢獻。逐分鐘及逐個設置地改變GCIB設備的操作條件可在GCIB中的中性單體及中性簇分量上產生變異。這些變異可產生製程變異,當該劑量測定法係藉由束電流測量進行時,其會較無法控制。 1) The dosimetry of the neutral beam accompanied by the use of a thermal sensor can make the dosimetry more accurate because it measures the total power of the beam. If conventional beam current measurements are used to do GCIB dosimetry, the dosimetry method will only measure and use the contribution of the ionized portion of the beam. Changing the operating conditions of the GCIB equipment minute by minute and one by one setting can produce variations in the neutral monomer and neutral cluster components in the GCIB. These variations can produce process variations, and when the dosimetry is performed by beam current measurement, it is less controllable.

2)使用中性束可處理廣泛多種材料,包括可由電荷效應損傷之高度絕緣材料及其它材料,不需要為了防止由該離子化束傳輸至工件之電荷讓工件帶電而提供標靶中和用電子來源。當使用習知GCIB時,中和標靶減低帶電咸少完美且該中和用電子來源其自身經常引進問題,諸如加熱工件、因在電子來源中的蒸發或濺射之污染等等。因為中性束不會將電荷傳輸至工件,此問題減少。 2) Using a neutral beam can process a wide variety of materials, including highly insulating materials and other materials that can be damaged by charge effects, and it is not necessary to provide target neutralization electrons in order to prevent the charge transmitted by the ionized beam to the workpiece from charging the workpiece source. When using conventional GCIB, the neutralization target reduces charged saltiness and is perfect and the neutralization electron source itself often introduces problems such as heating the workpiece, contamination due to evaporation or sputtering in the electron source, and so on. Because the neutral beam does not transfer charge to the workpiece, this problem is reduced.

3)不需要額外的裝置諸如大孔高強度磁鐵來從該中性束分離出高能量單體離子。在習知GCIB的情況中,傳輸至工件的高能量單體離子(及其它小簇離子)將滲透而產生 深層損傷的風險明顯,及例行上需要昂貴的磁性過濾器從該束中分離出此顆粒。在本文揭示出的中性束設備之情況中,從該束分離出全部離子來產生中性束將固有地移除全部單體離子。 3) No additional devices such as large-hole high-strength magnets are needed to separate high-energy monomer ions from the neutral beam. In the case of conventional GCIB, high-energy monomer ions (and other small cluster ions) transmitted to the workpiece will penetrate and be generated The risk of deep damage is obvious, and routinely requires expensive magnetic filters to separate the particles from the beam. In the case of the neutral beam apparatus disclosed herein, separating all ions from the beam to generate a neutral beam will inherently remove all monomer ions.

如於本文中所使用,當指出氣體簇尺度或氣體簇離子尺度時,用語”中尺度”意欲意謂著N=10至N=1500的尺度。 As used herein, when referring to the gas cluster scale or gas cluster ion scale, the term “medium scale” is intended to mean a scale of N=10 to N=1500.

如於本文中所使用,用語”GCIB”、”氣體簇離子束”及”氣體簇離子”意欲不僅包括離子化束及離子而且亦包括經加速的束及離子,其具有其在加速後經修改(包括中和)之全部或部分電荷狀態。用語”GCIB”及”氣體簇離子束”意欲包括全部束,其包含經加速的氣體簇,縱使它們亦可包含未團簇化的顆粒。如於本文中所使用,用語”中性束”意欲意謂著來自加速的氣體簇離子束之中性氣體簇及/或中性單體束,及其中該加速產生自氣體簇離子束之加速。 As used herein, the terms "GCIB", "gas cluster ion beam", and "gas cluster ion" are intended to include not only ionized beams and ions but also accelerated beams and ions, which have their modifications after acceleration (Including neutralization) all or part of the charge state. The terms "GCIB" and "gas cluster ion beam" are intended to include all beams, which include accelerated gas clusters, even though they may also contain unclustered particles. As used herein, the term "neutral beam" is intended to mean a neutral gas cluster and/or neutral monomer beam from an accelerated gas cluster ion beam, and where the acceleration is generated from the acceleration of the gas cluster ion beam .

如於本文中所使用,在參照於氣體中的顆粒或於束中的顆粒時,用語”單體”相等地指為單一原子或單一分子。用語”原子”、”分子”及”單體”可互換地使用及全部指為具有在討論下之氣體特徵的適當單體(簇的組分、簇離子的組分、或原子或分子)。例如,單原子氣體如氬可就原子、分子或單體來指出,及那些用語各者意謂著單一原子。同樣地,在二原子氣體如氮的情況中,其可就原子、分子或單體來指出,各者用語意謂著二原子分子。再 者,分子氣體如CO2或B2H6,可就原子、分子或單體來指出,各者用語意謂著多原子分子。使用這些慣例來簡化氣體及氣體簇或氣體簇離子的一般討論,其與它們是否呈其單原子、二原子或分子氣體形式無關。在參照分子或固體材料的構成物時,”原子”具有其習知意義。 As used herein, the term "monomer" refers equally to a single atom or a single molecule when referring to particles in a gas or particles in a beam. The terms "atom", "molecule" and "monomer" are used interchangeably and all refer to appropriate monomers (components of clusters, components of cluster ions, or atoms or molecules) having the gas characteristics under discussion. For example, monatomic gases such as argon can be specified in terms of atoms, molecules, or monomers, and each of those terms means a single atom. Similarly, in the case of a diatomic gas such as nitrogen, it can be indicated in terms of atoms, molecules or monomers, each term meaning a diatomic molecule. Furthermore, molecular gases such as CO 2 or B 2 H 6 can be specified in terms of atoms, molecules, or monomers, and each term means a polyatomic molecule. Use these conventions to simplify the general discussion of gases and gas clusters or gas cluster ions, regardless of whether they are in their monoatomic, diatomic, or molecular gas form. When referring to the structure of a molecule or solid material, "atom" has its conventional meaning.

100‧‧‧先前技藝的GCIB處理設備 100‧‧‧Previous GCIB processing equipment

102‧‧‧低壓容器 102‧‧‧Low pressure container

104‧‧‧噴嘴艙 104‧‧‧ Nozzle compartment

106‧‧‧離子化/加速艙 106‧‧‧Ionization/acceleration chamber

107‧‧‧束線艙 107‧‧‧ Harness module

108‧‧‧處理艙 108‧‧‧ processing cabin

110‧‧‧噴嘴 110‧‧‧ nozzle

111‧‧‧氣體儲存圓筒 111‧‧‧Gas storage cylinder

112‧‧‧可凝性來源氣體 112‧‧‧Condensable source gas

113‧‧‧氣體計量供給閥 113‧‧‧Gas metering supply valve

114‧‧‧進料管 114‧‧‧ Feeding tube

116‧‧‧停滯艙 116‧‧‧Stall module

118‧‧‧超音波噴射氣體 118‧‧‧ Ultrasonic jet gas

120‧‧‧氣體漏杓孔 120‧‧‧Gas scoop hole

122‧‧‧電離器 122‧‧‧Ionizer

124‧‧‧白熾燈絲 124‧‧‧ Incandescent filament

126‧‧‧電離器出口孔 126‧‧‧Ionizer outlet

128‧‧‧GCIB 128‧‧‧GCIB

130‧‧‧靜電掃描板 130‧‧‧Electrostatic scanning board

132‧‧‧靜電掃描板 132‧‧‧ electrostatic scanning board

134‧‧‧陽極電源供應器 134‧‧‧Anode power supply

136‧‧‧燈絲電源供應器 136‧‧‧Filament power supply

138‧‧‧遏止電源供應器 138‧‧‧Stop power supply

140‧‧‧加速器電源供應器 140‧‧‧Accelerator power supply

142‧‧‧遏止電極 142‧‧‧Stop electrode

144‧‧‧接地電極 144‧‧‧Ground electrode

146a‧‧‧真空泵 146a‧‧‧Vacuum pump

146b‧‧‧真空泵 146b‧‧‧Vacuum pump

146c‧‧‧真空泵 146c‧‧‧Vacuum pump

148‧‧‧GCIB 148‧‧‧GCIB

154‧‧‧軸 154‧‧‧axis

156‧‧‧掃描產生器 156‧‧‧scan generator

158‧‧‧導線對 158‧‧‧Wire pair

159‧‧‧導線對 159‧‧‧Wire pair

160‧‧‧工件 160‧‧‧Workpiece

162‧‧‧工件座 162‧‧‧Workpiece seat

164‧‧‧電絕緣器 164‧‧‧Electrical insulator

168‧‧‧電導線 168‧‧‧Electrical wire

170‧‧‧劑量處理器 170‧‧‧Dose processor

172‧‧‧束閘 172‧‧‧ beam brake

174‧‧‧連桿組 174‧‧‧Link

200‧‧‧另一種先前技藝GCIB處理設備 200‧‧‧Another prior art GCIB processing equipment

202‧‧‧工件座 202‧‧‧Workpiece seat

204‧‧‧鉸接/轉動機制 204‧‧‧ articulation/rotation mechanism

206‧‧‧縱軸 206‧‧‧Vertical axis

208‧‧‧軸 208‧‧‧axis

210‧‧‧旋轉動作 210‧‧‧rotation

212‧‧‧鉸接動作 212‧‧‧ articulated action

214‧‧‧掃描束限定孔 214‧‧‧ Scanning beam limited hole

216‧‧‧法拉第杯 216‧‧‧Faraday Cup

218‧‧‧絕緣器 218‧‧‧Insulator

220‧‧‧支撐成員 220‧‧‧ Supporting members

222‧‧‧電導線 222‧‧‧Electrical wire

224‧‧‧電導線 224‧‧‧Electrical wire

300‧‧‧中性束處理設備 300‧‧‧Neutral beam processing equipment

302‧‧‧偏轉板 302‧‧‧Deflector

304‧‧‧偏轉板 304‧‧‧deflection plate

306‧‧‧偏轉板電源供應器 306‧‧‧Deflector power supply

308‧‧‧電導線 308‧‧‧Electrical wire

310‧‧‧電流感應器/顯示器 310‧‧‧current sensor/display

312‧‧‧電導線 312‧‧‧Electrical wire

314‧‧‧加速的中性束 314‧‧‧Accelerated neutral beam

316‧‧‧離子化部分 316‧‧‧Ionized part

320‧‧‧電流感應器/顯示器 320‧‧‧current sensor/display

330‧‧‧壓力感應器 330‧‧‧ pressure sensor

332‧‧‧電纜 332‧‧‧Cable

334‧‧‧壓力感應器控制器 334‧‧‧ pressure sensor controller

336‧‧‧束閘控制器 336‧‧‧ beam brake controller

338‧‧‧連桿組 338‧‧‧Link

400‧‧‧中性束處理設備 400‧‧‧Neutral beam processing equipment

402‧‧‧熱感應器 402‧‧‧thermal sensor

404‧‧‧低導熱度附件 404‧‧‧Low thermal conductivity accessories

406‧‧‧路徑 406‧‧‧ Path

408‧‧‧致動器 408‧‧‧Actuator

410‧‧‧轉動式支撐臂 410‧‧‧rotating support arm

412‧‧‧樞軸 412‧‧‧Pivot

414‧‧‧停放位置 414‧‧‧Parking position

416‧‧‧可逆式旋轉動作 416‧‧‧Reversible rotation action

418‧‧‧電纜 418‧‧‧Cable

420‧‧‧熱感應器控制器 420‧‧‧thermal sensor controller

422‧‧‧電流感應器 422‧‧‧current sensor

424‧‧‧束電流測量裝置 424‧‧‧Beam current measuring device

426‧‧‧電纜 426‧‧‧Cable

428‧‧‧電纜 428‧‧‧Cable

430‧‧‧電纜 430‧‧‧Cable

432‧‧‧劑量測定控制器 432‧‧‧Dose determination controller

434‧‧‧連桿組 434‧‧‧Link set

440‧‧‧偏轉板電源供應器 440‧‧‧Deflector power supply

442‧‧‧電纜 442‧‧‧Cable

500‧‧‧中性束處理設備 500‧‧‧Neutral beam processing equipment

502‧‧‧電子遏止柵電極 502‧‧‧electron suppression gate electrode

504‧‧‧絕緣支撐 504‧‧‧Insulation support

506‧‧‧第二遏止電源供應器 506‧‧‧Second stop power supply

550‧‧‧中性束處理設備 550‧‧‧Neutral beam processing equipment

556‧‧‧樣品 556‧‧‧Sample

558‧‧‧法拉第杯 558‧‧‧Faraday Cup

560‧‧‧電導線 560‧‧‧Electrical wire

562‧‧‧電流感應器 562‧‧‧current sensor

564‧‧‧電纜 564‧‧‧Cable

566‧‧‧劑量測定控制器 566‧‧‧ Dosimetry Controller

600‧‧‧中性束處理設備 600‧‧‧Neutral beam processing equipment

602‧‧‧機械式掃瞄器 602‧‧‧Mechanical Scanner

604‧‧‧致動器基座 604‧‧‧Actuator base

606‧‧‧Y位移臺 606‧‧‧Y stage

608‧‧‧X位移臺 608‧‧‧X stage

610‧‧‧Y方向 610‧‧‧Y direction

612‧‧‧X方向 612‧‧‧X direction

614‧‧‧絕緣器 614‧‧‧Insulator

616‧‧‧工件座 616‧‧‧Workpiece holder

618‧‧‧機械式掃描控制器 618‧‧‧ mechanical scanning controller

620‧‧‧電纜 620‧‧‧Cable

622‧‧‧電纜 622‧‧‧Cable

628‧‧‧劑量測定控制器 628‧‧‧Dose determination controller

700‧‧‧中性束處理設備 700‧‧‧Neutral beam processing equipment

702‧‧‧氣體瓶 702‧‧‧gas bottle

704‧‧‧束線氣體 704‧‧‧beam gas

706‧‧‧洩漏閥 706‧‧‧Leak valve

708‧‧‧氣體進料管 708‧‧‧Gas feed pipe

710‧‧‧氣體擴散器 710‧‧‧Gas diffuser

716‧‧‧壓力控制器 716‧‧‧Pressure controller

800‧‧‧中性束處理設備 800‧‧‧ Neutral beam processing equipment

802‧‧‧反射電極 802‧‧‧Reflective electrode

804‧‧‧實質上透明的電網電極 804‧‧‧ Substantially transparent grid electrode

806‧‧‧電導線 806‧‧‧Electrical wire

808‧‧‧電導線 808‧‧‧Electrical wire

810‧‧‧鏡子電源供應器 810‧‧‧Mirror power supply

812‧‧‧法拉第杯 812‧‧‧Faraday Cup

814‧‧‧離子化部分 814‧‧‧Ionized part

816‧‧‧遏止電極網柵電極 816‧‧‧Retaining electrode grid electrode

820‧‧‧電導線 820‧‧‧Electrical wire

822‧‧‧第三遏止電源供應器 822‧‧‧The third containment power supply

824‧‧‧電流感應器 824‧‧‧current sensor

826‧‧‧電導線 826‧‧‧Electrical wire

830‧‧‧劑量測定控制器 830‧‧‧Dose determination controller

836‧‧‧孔洞 836‧‧‧hole

838‧‧‧孔洞 838‧‧‧hole

840‧‧‧電纜 840‧‧‧Cable

940‧‧‧中性束處理設備 940‧‧‧ Neutral beam processing equipment

942‧‧‧阻滯電壓電源供應器 942‧‧‧block voltage power supply

944‧‧‧加速電源供應器 944‧‧‧Accelerated power supply

946‧‧‧劑量測定控制器 946‧‧‧Dose determination controller

948‧‧‧加速電極 948‧‧‧Accelerating electrode

950‧‧‧永久磁鐵陣列 950‧‧‧Permanent magnet array

952‧‧‧阻滯電極 952‧‧‧Blocking electrode

954‧‧‧導電支撐成員 954‧‧‧ conductive support member

956‧‧‧電纜 956‧‧‧Cable

958‧‧‧離子化部分 958‧‧‧Ionized part

960‧‧‧中性束處理設備 960‧‧‧Neutral beam processing equipment

962‧‧‧接地電極 962‧‧‧Ground electrode

980‧‧‧中性束處理設備 980‧‧‧Neutral beam processing equipment

982‧‧‧磁分析器 982‧‧‧Magnetic analyzer

984‧‧‧支撐 984‧‧‧Support

986‧‧‧擋板 986‧‧‧Baffle

988‧‧‧中性束孔 988‧‧‧Neutral beam hole

990‧‧‧離子化部分 990‧‧‧Ionized part

1000‧‧‧TEM影像 1000‧‧‧TEM image

1002‧‧‧單晶矽 1002‧‧‧Single crystal silicon

1004‧‧‧非晶相區域 1004‧‧‧Amorphous phase region

1006‧‧‧環氧樹脂外罩 1006‧‧‧Epoxy cover

1008‧‧‧粗糙界面 1008‧‧‧Rough interface

1020‧‧‧TEM影像 1020‧‧‧TEM image

1022‧‧‧單晶矽 1022‧‧‧Single crystal silicon

1024‧‧‧非晶相區域 1024‧‧‧Amorphous phase region

1026‧‧‧環氧樹脂外罩 1026‧‧‧Epoxy cover

1028‧‧‧粗糙界面 1028‧‧‧Rough interface

1040‧‧‧TEM影像 1040‧‧‧TEM image

1042‧‧‧單晶矽 1042‧‧‧Single crystal silicon

1044‧‧‧非晶相區域 1044‧‧‧Amorphous phase region

1046‧‧‧環氧樹脂外罩 1046‧‧‧Epoxy cover

1048‧‧‧平滑界面 1048‧‧‧Smooth interface

1060‧‧‧曲線圖 1060‧‧‧ Curve

1062‧‧‧硼濃度 1062‧‧‧Boron concentration

1100‧‧‧TEM影像 1100‧‧‧TEM image

1102‧‧‧單晶矽 1102‧‧‧Single crystal silicon

1104‧‧‧非晶相區域 1104‧‧‧Amorphous phase region

1106‧‧‧環氧樹脂外罩 1106‧‧‧Epoxy cover

1108‧‧‧平滑界面 1108‧‧‧Smooth interface

1200‧‧‧深度曲線測量曲線圖 1200‧‧‧Depth curve measurement curve

1202‧‧‧高原區 1202‧‧‧ Plateau

1204‧‧‧區域 1204‧‧‧Region

1220‧‧‧TEM影像 1220‧‧‧TEM image

1222‧‧‧矽基材 1222‧‧‧Silicon substrate

1224‧‧‧原始氧化物膜 1224‧‧‧Original oxide film

1226‧‧‧環氧樹脂外罩 1226‧‧‧Epoxy cover

1240‧‧‧TEM影像 1240‧‧‧TEM image

1242‧‧‧結晶矽材料 1242‧‧‧crystalline silicon material

1244‧‧‧非晶相膜 1244‧‧‧Amorphous phase film

1246‧‧‧環氧樹脂外罩 1246‧‧‧Epoxy cover

1248‧‧‧平滑界面 1248‧‧‧Smooth interface

1260‧‧‧TEM影像 1260‧‧‧TEM image

1262‧‧‧結晶矽材料 1262‧‧‧crystalline silicon material

1264‧‧‧氧化物膜 1264‧‧‧oxide film

1266‧‧‧環氧樹脂外罩 1266‧‧‧Epoxy cover

1268‧‧‧平滑界面 1268‧‧‧Smooth interface

1280‧‧‧TEM影像 1280‧‧‧TEM image

1282‧‧‧結晶矽材料 1282‧‧‧crystalline silicon material

1284‧‧‧氧化物膜 1284‧‧‧oxide film

1286‧‧‧環氧樹脂外罩 1286‧‧‧Epoxy cover

1288‧‧‧平滑界面 1288‧‧‧Smooth interface

1300‧‧‧深度曲線測量曲線圖 1300‧‧‧Depth curve measurement curve

1302‧‧‧平坦區域 1302‧‧‧flat area

1304‧‧‧區域 1304‧‧‧Region

1320‧‧‧映圖 1320‧‧‧ map

1322‧‧‧凸點 1322‧‧‧Bump

1340‧‧‧映圖 1340‧‧‧ map

1400‧‧‧圖式 1400‧‧‧schema

1402‧‧‧光學基材 1402‧‧‧Optical substrate

1404‧‧‧光學塗佈材料 1404‧‧‧Optical coating materials

1406‧‧‧界面 1406‧‧‧Interface

1410‧‧‧圖式 1410‧‧‧schema

1412‧‧‧束 1412‧‧‧ bundle

1420‧‧‧圖式 1420‧‧‧schema

1422‧‧‧混合物區域 1422‧‧‧mix area

1430‧‧‧圖式 1430‧‧‧schema

1432‧‧‧光學塗佈材料 1432‧‧‧Optical coating materials

1500‧‧‧圖式 1500‧‧‧schema

1502‧‧‧矽基材 1502‧‧‧Silicon substrate

1510‧‧‧圖式 1510‧‧‧schema

1512‧‧‧束 1512‧‧‧ bundle

1520‧‧‧圖式 1520‧‧‧schema

1522‧‧‧植入層 1522‧‧‧Implanted layer

1530‧‧‧圖式 1530‧‧‧schema

1532‧‧‧經退火經熱處理層 1532‧‧‧Annealed and heat-treated layer

1600‧‧‧圖式 1600‧‧‧schema

1602‧‧‧矽基材 1602‧‧‧Silicon substrate

1604‧‧‧接觸式樣板 1604‧‧‧Contact model

1610‧‧‧圖式 1610‧‧‧schema

1612‧‧‧束 1612‧‧‧ bundle

1614‧‧‧地區及/或區域 1614‧‧‧ region and/or region

1620‧‧‧圖式 1620‧‧‧schema

1622‧‧‧投影式樣板 1622‧‧‧Projection model

1630‧‧‧圖式 1630‧‧‧schema

1632‧‧‧溝槽 1632‧‧‧Groove

1634‧‧‧中性束 1634‧‧‧neutral beam

1640‧‧‧圖式 1640‧‧‧schema

1642‧‧‧蝕刻束 1642‧‧‧Etching beam

1644‧‧‧高原區 1644‧‧‧ Plateau

1650‧‧‧圖式 1650‧‧‧schema

1652‧‧‧硬遮罩層 1652‧‧‧hard mask layer

1660‧‧‧圖式 1660‧‧‧schema

1662‧‧‧地區 1662‧‧‧ District

1664‧‧‧硬遮罩區域 1664‧‧‧hard mask area

1670‧‧‧圖式 1670‧‧‧schema

1672‧‧‧矽表面 1672‧‧‧Silicon surface

VA‧‧‧陽極電壓 V A ‧‧‧Anode voltage

Vf‧‧‧燈絲電壓 V f ‧‧‧ filament voltage

VS‧‧‧遏止電壓 V S ‧‧‧ Suppression voltage

VAcc‧‧‧加速電壓 V Acc ‧‧‧ acceleration voltage

PB‧‧‧壓力 P B ‧‧‧ pressure

VD‧‧‧正偏轉電壓 V D ‧‧‧ Positive deflection voltage

ID‧‧‧電流 I D ‧‧‧ current

IB‧‧‧GCIB束電流 I B ‧‧‧GCIB beam current

VS2‧‧‧第二遏止電壓 V S2 ‧‧‧Second stop voltage

IS‧‧‧樣品電流 I S ‧‧‧ sample current

VM‧‧‧鏡子電壓 V M ‧‧‧Mirror voltage

VR‧‧‧阻滯電位 V R ‧‧‧ Blocking potential

VS3‧‧‧負第三遏止電壓 V S3 ‧‧‧Negative third suppression voltage

ID2‧‧‧法拉第杯電流 I D2 ‧‧‧ Faraday Cup current

為了較好地一起了解本發明與其它及其進一步目標,參照伴隨的圖形,其中:圖1係一先前技藝圖式,其闡明使用GCIB來處理工件的設備之元件;圖2係另一種先前技藝圖式,其闡明使用GCIB來處理工件的設備之元件,其使用掃描式離子束及操控該工件;圖3係根據本發明的具體實例之設備的圖式,其使用靜電偏轉板來分離該帶電與未帶電束組分;圖4係根據本發明的具體實例之設備的圖式,其使用一用於中性束測量之熱感應器;圖5係根據本發明的具體實例之設備的圖式,其使用在遏止偏轉板上所收集之經偏轉的離子束電流作為劑量測定方法之組分;圖6係根據本發明的具體實例之設備的圖式,其使用在法拉第杯中所收集之經偏轉的離子束樣品作為劑量測定方法之組分;圖7顯示出根據本發明的具體實例之設備的圖式,其使用中性束均勻地機械式掃描照射延伸開的工件; 圖8顯示出根據本發明的具體實例之設備的圖式,其使用將氣體注射進該束線艙中來控制該氣體標靶厚度之工具;圖9顯示出根據本發明的具體實例之設備的圖式,其使用靜電鏡來分離帶電與中性束組分;圖10顯示出根據本發明的具體實例之設備的圖式,其中使用加速-減速組態來分離該帶電束與該中性束組分;圖11顯示出根據本發明的具體實例之設備的圖式,其中使用另一種加速-減速組態來分離該帶電束與該中性束組分;圖12A、12B、12C及12D顯示出處理結果,其指示出與以完整的GCIB或該束的帶電組分處理比較,藉由束的中性組分來處理金屬膜會產生該膜的優異平滑化;圖13A及13B顯示出在表現出藥物溶析醫療裝置的鈷-鉻試樣上之藥物塗層比較,其中以中性束處理產生比以完整的GCIB處理優異的結果;圖14係根據本發明的具體實例之中性束處理設備的圖式,其使用磁性分離;圖15A、15B及15C係TEM影像,其闡明如與氣體簇離子束比較,當使用本發明之中性束具體實例時所產生的優異界面;圖16係一使用本發明的具體實例之曲線圖,其顯示出合適於形成淺接面的淺硼植入之SIMS曲線;圖17係一TEM影像,其顯示出當使用本發明的具體實 例來形成摻雜硼的半導體時,所形成之高品質界面;圖18係一使用本發明的具體實例之曲線圖,其闡明SiO2及Si之蝕刻;圖19A及19B係TEM影像,其闡明使用本發明的具體實例在半導體材料中形成非晶相層;圖20A及20B係TEM影像,其闡明應用來自GCIBs之加速的中性束在半導體中形成膜;圖21係一曲線圖,其闡明使用來自加速的GCIB之加速的中性束在矽基材上沈積鑽石狀碳膜;圖22係一乾淨、經習知拋光的光學玻璃表面之粗糙度的原子力顯微圖映圖,其顯示出粗糙度程度、缺乏平面性及存在凸點;圖23係一光學玻璃表面,其在根據本發明的具體實例使用來自加速的GCIB之加速的中性束進行平滑化後之原子力顯微圖映圖;圖24A、24B、24C及24D係一圖式,其顯示出使用來自GCIB之加速的中性束或使用GCIB在光學基材上製造光學塗層之方法的步驟,其中與習知技術比較,根據本發明的具體實例,該塗層對基材具有優異的黏附力;圖25A及25B係未處理的LBO光學構件之表面原子力顯微圖映圖,其顯示出由於大氣曝露而降解;圖26A及26B係使用來自GCIB之加速的中性束進行處理之LBO光學構件的表面原子力顯微圖映圖,其顯示出在根據本發明的具體實例之處理後,對由於大氣曝露的降解 造成減低;圖27A、27B、27C及27D係一圖式,其顯示出使用來自GCIB之加速的中性束在矽基材上形成SiC或SiCx層之方法的步驟;及圖28A、28B、28C、28D、28E、28F、28G及28H係一圖式,其顯示出使用來自GCIB之加速的中性束在基材上形成硬遮罩圖案之方法的步驟,其沒有如某些裝置之先進的微製造所需要般使用光阻。 For a better understanding of the present invention and others and their further objectives, refer to the accompanying figures, where: Figure 1 is a prior art diagram illustrating the components of equipment that uses GCIB to process a workpiece; Figure 2 is another prior art The drawing, which illustrates the elements of a device that uses GCIB to process a workpiece, uses a scanning ion beam and manipulates the workpiece; FIG. 3 is a drawing of a device according to a specific example of the present invention, which uses an electrostatic deflection plate to separate the charged And uncharged beam components; FIG. 4 is a diagram of a device according to a specific example of the present invention, which uses a thermal sensor for neutral beam measurement; FIG. 5 is a diagram of a device according to a specific example of the present invention , Which uses the deflected ion beam current collected on the containment deflection plate as a component of the dosimetry method; FIG. 6 is a diagram of equipment according to a specific example of the present invention, which uses the collected experience in the Faraday cup The deflected ion beam sample is used as a component of the dosimetry method; FIG. 7 shows a diagram of a device according to a specific example of the present invention, which uses a neutral beam to uniformly mechanically scan an extended workpiece; FIG. 8 shows The drawing of the equipment of the specific example of the present invention, which uses a tool for injecting gas into the beam compartment to control the thickness of the gas target; FIG. 9 shows the drawing of the equipment of the specific example of the present invention, which uses Electrostatic mirror to separate charged and neutral beam components; FIG. 10 shows a diagram of a device according to a specific example of the present invention, wherein an acceleration-deceleration configuration is used to separate the charged beam and the neutral beam components; FIG. 11 A diagram showing a device according to a specific example of the present invention, wherein another acceleration-deceleration configuration is used to separate the charged beam and the neutral beam components; FIGS. 12A, 12B, 12C, and 12D show the processing results, which Indicate that the treatment of the metal film with the neutral component of the beam will result in excellent smoothing of the film compared to the treatment with the complete GCIB or the charged component of the beam; Figures 13A and 13B show Comparison of drug coatings on cobalt-chromium samples of medical devices, where neutral beam treatment produces superior results than complete GCIB treatment; Figure 14 is a diagram of a neutral beam treatment device according to a specific example of the invention , Which uses magnetic separation; FIGS. 15A, 15B, and 15C are TEM images, which illustrate the excellent interface produced when using the specific example of the neutral beam of the present invention as compared with a gas cluster ion beam; FIG. 16-using the present invention A specific example of a graph showing a SIMS curve suitable for shallow boron implantation to form a shallow junction; FIG. 17 is a TEM image showing when a specific example of the present invention is used to form a boron-doped semiconductor , High-quality interface formed; FIG. 18 is a graph using a specific example of the present invention, which illustrates the etching of SiO2 and Si; FIGS. 19A and 19B are TEM images, which illustrate the specific example of using the present invention in semiconductor materials Formation of an amorphous phase layer; Figures 20A and 20B are TEM images illustrating the application of accelerated neutral beams from GCIBs to form a film in a semiconductor; Figure 21 is a graph illustrating the use of The accelerated neutral beam of self-accelerated GCIB deposits a diamond-like carbon film on a silicon substrate; Figure 22 is an atomic force micrograph of the roughness of a clean, conventionally polished optical glass surface, showing roughness Degree, lack of planarity, and presence of bumps; FIG. 23 is an optical glass surface, which is an atomic force micrograph after smoothing using an accelerated neutral beam from accelerated GCIB according to a specific example of the present invention; 24A, 24B, 24C, and 24D are diagrams showing the steps of a method of manufacturing an optical coating on an optical substrate using an accelerated neutral beam from GCIB or using GCIB, in comparison with conventional techniques, according to A specific example of the present invention, the coating has excellent adhesion to the substrate; Figures 25A and 25B are surface atomic force micrographs of untreated LBO optical components, which show degradation due to atmospheric exposure; Figure 26A and 26B is a surface atomic force micrograph of an LBO optical component treated with an accelerated neutral beam from GCIB, which shows a reduction in degradation due to atmospheric exposure after treatment according to a specific example of the invention; 27A, 27B, 27C, and 27D are diagrams showing the steps of a method of forming an SiC or SiC x layer on a silicon substrate using an accelerated neutral beam from GCIB; and FIGS. 28A, 28B, 28C, 28D, 28E, 28F, 28G, and 28H are diagrams showing the steps of a method of forming a hard mask pattern on a substrate using an accelerated neutral beam from GCIB, which does not have advanced microfabrication facilities like some devices Use photoresist as needed.

較佳實施例之詳細說明 Detailed description of the preferred embodiment

現在參照圖1,其顯示出先前技藝之GCIB處理設備100的圖式組態。低壓容器102具有三個流體連接艙:噴嘴艙104、離子化/加速艙106及處理艙108。三個艙各別藉由真空泵146a、146b及146c抽空。貯存在氣體儲存圓筒111中之經加壓的可凝性來源氣體112(例如,氬)流過氣體計量供給閥113及進料管114進入停滯艙116中。在停滯艙116中的壓力(典型為幾個大氣壓)造成氣體經由噴嘴110噴入實質上較低壓力的真空中,造成形成超音波噴射氣體118。在噴射時膨脹產生冷卻,此造成一部分的噴射氣體118凝結成簇,每個簇由數個至數千個弱束縛的原子或分子組成。使用氣體漏杓孔120,藉由從該噴射簇中部分分離出尚未凝結進噴射簇中之氣體分子來控制流進下游艙中的氣體。在下游艙中過多的壓力可因為干擾該氣體簇離子之傳輸及因為干擾可使用於束形成及傳輸的高電壓之管理 而係有害。合適的可凝性來源氣體112包括但不限於氬及其它可凝性惰性氣體、氮、二氧化碳、氧、及許多其它氣體及/或氣體混合物。在超音波噴射氣體118中形成該氣體簇後,至少一部分的氣體簇於電離器122中離子化,其中該電離器典型為一電子衝擊式電離器,其藉由從一或多個白熾燈絲124熱發射(或從其它合適的電子來源)產生電子,及加速並引導該電子使其能夠與在噴射氣體118中的氣體簇碰撞。電子與氣體簇衝擊會從該氣體簇的某些部分噴出電子造成那些簇變成正離子化。某些簇可噴出多於一個電子及可變成多重離子化。控制在加速後之電子數目及其能量典型可影響將發生的離子化數目及在該氣體簇的多重與單一離子化間之比率。遏止電極142及接地電極144從該電離器出口孔126引出簇離子,將其加速至想要的能量(典型使用數百伏至數十千伏的加速電壓),及將其聚焦以形成GCIB 128。在該電離器出口孔126與遏止電極142間,該GCIB 128橫越之區域指為引出區域。包含氣體簇的超音波噴射氣體118之軸(在噴嘴110處決定)實質上與GCIB 128的軸154相同。燈絲電源供應器136提供燈絲電壓Vf來加熱該電離器燈絲124。陽極電源供應器134提供陽極電壓VA以加速從燈絲124發射出的熱電子,以使得該熱電子照射該含簇噴射氣體118而產生簇離子。遏止電源供應器138供應遏止電壓VS(級數數百至幾千伏特)以對遏止電極142施加偏壓。加速器電源供應器140供應加速電壓VAcc以相對於遏止電極142及接地電極144對該電離器122施加偏壓,以便 產生等於VAcc的總GCIB加速電壓。遏止電極142提供從該電離器122的電離器出口孔126引出離子及防止不想要的電子從下游進入電離器122及形成聚焦的GCIB 128。 Referring now to FIG. 1, it shows a schematic configuration of the GCIB processing apparatus 100 of the prior art. The low-pressure vessel 102 has three fluid connection compartments: a nozzle compartment 104, an ionization/acceleration compartment 106, and a processing compartment 108. The three compartments are evacuated by vacuum pumps 146a, 146b and 146c. The pressurized condensable source gas 112 (for example, argon) stored in the gas storage cylinder 111 flows through the gas metering supply valve 113 and the feed pipe 114 into the stagnation chamber 116. The pressure in the stagnation chamber 116 (typically a few atmospheres) causes the gas to be sprayed through the nozzle 110 into a substantially lower pressure vacuum, resulting in the formation of ultrasonic spray gas 118. The expansion during the injection generates cooling, which causes a portion of the injection gas 118 to condense into clusters, each cluster consisting of several to thousands of weakly bound atoms or molecules. The gas skimmer hole 120 is used to control the gas flowing into the downstream chamber by partially separating gas molecules that have not condensed into the spray cluster from the spray cluster. Too much pressure in the downstream compartment can be harmful because it interferes with the transmission of the gas cluster ions and because the interference can cause the management of high voltages used for beam formation and transmission. Suitable condensable source gases 112 include, but are not limited to, argon and other condensable inert gases, nitrogen, carbon dioxide, oxygen, and many other gases and/or gas mixtures. After the gas cluster is formed in the ultrasonic jet gas 118, at least a portion of the gas cluster is ionized in the ionizer 122, wherein the ionizer is typically an electron impact ionizer, which consists of one or more incandescent filaments 124 Thermal emission (or from other suitable electron sources) generates electrons, and accelerates and directs the electrons so that they can collide with the gas cluster in the spray gas 118. The impact of electrons and gas clusters will eject electrons from certain parts of the gas cluster, causing those clusters to become positively ionized. Some clusters can eject more than one electron and can become multiple ionized. Controlling the number of electrons and their energy after acceleration can typically affect the number of ionizations that will occur and the ratio between the multiple and single ionization of the gas cluster. The containment electrode 142 and the ground electrode 144 extract cluster ions from the ionizer exit hole 126, accelerate them to the desired energy (typically using accelerating voltages of hundreds of volts to tens of kilovolts), and focus them to form GCIB 128 . Between the ionizer outlet hole 126 and the containment electrode 142, the area where the GCIB 128 traverses is referred to as the lead-out area. The axis of the ultrasonic jet gas 118 (determined at the nozzle 110) containing the gas cluster is substantially the same as the axis 154 of the GCIB 128. The filament power supply 136 provides a filament voltage V f to heat the ionizer filament 124. Anode power supply 134 provides voltage V A of the anode to accelerate the electrons emitted from the hot filament 124, so that the hot electrons generated by irradiating the cluster ions cluster containing gas jet 118. The containment power supply 138 supplies a containment voltage V S (several hundreds to thousands of volts) to bias the containment electrode 142. The accelerator power supply 140 supplies an acceleration voltage V Acc to bias the ionizer 122 with respect to the stop electrode 142 and the ground electrode 144 so as to generate a total GCIB acceleration voltage equal to V Acc . The containment electrode 142 provides extraction of ions from the ionizer exit hole 126 of the ionizer 122 and prevents unwanted electrons from entering the ionizer 122 downstream and forming a focused GCIB 128.

將工件160保持在工件座162上,其中該工件可係(例如)欲藉由GCIB處理進行處理的醫療裝置、半導體材料、光學元件或其它工件,其中該工件座將該工件佈置在GCIB 128之路徑中。該工件座係接附至處理艙108,但是藉由電絕緣器164與其電絕緣。因此,攻擊工件160及工件座162的GCIB 128流過電導線168至劑量處理器170。束閘172控制GCIB 128沿著軸154傳送至工件160。束閘172典型具有打開狀態及關閉狀態,其係由連桿組174控制,其中該控制可係(例如)電、機械式或電機式。該劑量處理器170控制束閘172的打開/關閉狀態以管理由工件160及工件座162接收的GCIB劑量。在操作時,該劑量處理器170打開束閘172以起始工件160的GCIB照射。劑量處理器170典型對到達工件160及工件座162的GCIB電流進行積分以計算所累積的GCIB照射劑量。在預定劑量下,當已經達到預定劑量時,劑量處理器170關閉束閘172,終止處理。 The workpiece 160 is held on a workpiece holder 162, where the workpiece may be, for example, a medical device, semiconductor material, optical element, or other workpiece to be processed by GCIB processing, wherein the workpiece holder arranges the workpiece on the GCIB 128 In the path. The workpiece holder is attached to the processing chamber 108, but is electrically insulated from it by an electrical insulator 164. Therefore, the GCIB 128 attacking the workpiece 160 and the workpiece holder 162 flows through the electrical wire 168 to the dose processor 170. The beam brake 172 controls the GCIB 128 to be transferred to the workpiece 160 along the axis 154. The beam brake 172 typically has an open state and a closed state, which are controlled by a linkage group 174, where the control may be, for example, electrical, mechanical, or motorized. The dose processor 170 controls the opening/closing state of the beam gate 172 to manage the GCIB dose received by the workpiece 160 and the workpiece holder 162. In operation, the dose processor 170 opens the beam shutter 172 to initiate GCIB irradiation of the workpiece 160. The dose processor 170 typically integrates the GCIB current reaching the workpiece 160 and the workpiece holder 162 to calculate the accumulated GCIB irradiation dose. At the predetermined dose, when the predetermined dose has been reached, the dose processor 170 closes the beam shutter 172 and terminates the process.

在下列描述中,為了簡化圖形,來自較早圖形的項目編號可沒有討論而顯露在隨後的圖形中。同樣地,所討論與較早圖形相關之項目可顯露在隨後的圖形中而沒有項目編號或額外的描述。在此情況中,具有類似編號的項目係類似的項目及具有先前描述的特徵與功能,及顯示在現存圖形中沒有項目編號之項目的闡明指為具有與在較 早編號的圖形中所闡明之類似項目相同的功能之類似項目。 In the following description, in order to simplify the figure, the item number from the earlier figure may be revealed in the subsequent figure without discussion. Likewise, the item in question related to the earlier graphic can be revealed in the subsequent graphic without the item number or additional description. In this case, the items with similar numbers are similar items and have the previously described features and functions, and the items shown in the existing figures without item numbers are clarified as having Similar items with the same function as the similar items explained in the drawing numbered earlier.

圖2顯示出一圖式,其闡明使用GCIB來處理工件之另一種先前技藝GCIB處理設備200的元件,其使用掃描該離子束及操控該工件。將欲藉由GCIB處理設備200處理的工件160保持在工件座202上,且配置在GCIB 128的路徑中。為了達成工件160的均勻處理,對工件座202進行設計以如均勻處理所需要般操控工件160。 FIG. 2 shows a diagram illustrating the elements of another prior art GCIB processing apparatus 200 that uses GCIB to process a workpiece, which uses scanning the ion beam and manipulating the workpiece. The workpiece 160 to be processed by the GCIB processing apparatus 200 is held on the workpiece holder 202 and is arranged in the path of the GCIB 128. In order to achieve uniform processing of the workpiece 160, the workpiece holder 202 is designed to manipulate the workpiece 160 as required for uniform processing.

任何非平面例如球形或杯狀、圓形、不規則或其它不平坦組態之工件表面可在相對於該束的入射呈一定角度範圍內進行定向,以獲得該工件表面的最理想GCIB處理。工件座202可完全鉸接,以將欲處理之全部非平面表面定向成與GCIB 128合適的排列,以提供處理最佳化及均勻性。更特別的是,當該欲處理的工件160係非平面時,該工件座202可藉由鉸接/轉動機制204,以旋轉動作210轉動及以鉸接動作212鉸動。該鉸接/轉動機制204可准許裝置繞著縱軸206(其係與GCIB 128的軸154同軸)轉動360度及繞著與軸206垂直的軸208充分鉸動,以將該工件表面維持在束入射之想要的範圍內。 Any non-planar workpiece surface such as spherical or cup-shaped, circular, irregular or other uneven configurations can be oriented at an angle with respect to the incidence of the beam to obtain the most ideal GCIB treatment of the workpiece surface. Workpiece holder 202 can be fully articulated to orient all non-planar surfaces to be processed in a suitable arrangement with GCIB 128 to provide processing optimization and uniformity. More specifically, when the workpiece 160 to be processed is non-planar, the workpiece holder 202 can be rotated by the rotation action 210 and the hinge action 212 by the hinge/rotation mechanism 204. The articulation/rotation mechanism 204 permits the device to rotate 360 degrees about the longitudinal axis 206 (which is coaxial with the axis 154 of the GCIB 128) and to fully pivot about the axis 208 perpendicular to the axis 206 to maintain the workpiece surface in the beam Within the desired range of incidence.

在某些條件下,依工件160的尺寸而定,可想要一掃描系統以產生大工件的均勻照射。雖然GCIB處理經常不需要,但可使用二對正交定向的靜電掃描板130及132在擴大的處理面積內產生光柵或其它掃描圖案。當進行此束掃描時,掃描產生器156透過導線對159對掃描板對132 提供X軸掃描信號電壓,及通過導線對158對掃描板對130提供Y軸掃描信號電壓。該掃描信號電壓通常係不同頻率的三角波,此使得GCIB 128被轉換成掃描式GCIB 148來掃描該工件160的全體表面。掃描束限定孔214界定出一掃描面積。該掃描束限定孔214導電及電連接至該低壓容器102壁及由支撐成員220支撐。該工件座202係經由可撓的電導線222電連接至法拉第杯216,其中該法拉第杯圍繞該工件160及工件座202且收集通過該限定孔214的全部電流。該工件座202係與該鉸接/轉動機制204電隔離,及法拉第杯216係藉由絕緣器218與低壓容器102電隔離及裝配至該容器。此外,來自掃描式GCIB 148且通過掃描束限定孔214的全部電流係收集在法拉第杯216中及流過電導線224至劑量處理器170。在操作時,該劑量處理器170打開束閘172以起始工件160的GCIB照射。劑量處理器170典型對到達該工件160及工件座202及法拉第杯216的GCIB電流進行積分以計算每單位面積所累積的GCIB照射劑量。在預定劑量下,當已經達成預定劑量時,該劑量處理器170關閉束閘172,終止處理。在預定劑量的累積期間,可藉由該鉸接/轉動機制204來操控工件160以保證處理全部想要的表面。 Under certain conditions, depending on the size of the workpiece 160, a scanning system may be desired to produce uniform illumination of large workpieces. Although GCIB processing is often not required, two pairs of orthogonally oriented electrostatic scanning plates 130 and 132 can be used to generate gratings or other scanning patterns within the enlarged processing area. When performing this beam scan, the scan generator 156 passes the wire pair 159 to the scanning board pair 132 The X-axis scanning signal voltage is provided, and the Y-axis scanning signal voltage is provided to the scanning board pair 130 through the wire pair 158. The scan signal voltage is usually a triangular wave of different frequencies, which causes the GCIB 128 to be converted into a scan type GCIB 148 to scan the entire surface of the workpiece 160. The scanning beam defining hole 214 defines a scanning area. The scanning beam defining hole 214 is electrically and electrically connected to the wall of the low-pressure container 102 and supported by the support member 220. The workpiece holder 202 is electrically connected to the Faraday cup 216 via a flexible electrical wire 222, wherein the Faraday cup surrounds the workpiece 160 and the workpiece holder 202 and collects all current passing through the defining hole 214. The workpiece holder 202 is electrically isolated from the hinge/rotation mechanism 204, and the Faraday cup 216 is electrically isolated from and assembled to the low-pressure container 102 by an insulator 218. In addition, all the current from the scanning GCIB 148 and through the scanning beam defining hole 214 is collected in the Faraday cup 216 and flows through the electrical lead 224 to the dose processor 170. In operation, the dose processor 170 opens the beam shutter 172 to initiate GCIB irradiation of the workpiece 160. The dose processor 170 typically integrates the GCIB current reaching the workpiece 160 and the workpiece holder 202 and the Faraday cup 216 to calculate the accumulated GCIB irradiation dose per unit area. At the predetermined dose, when the predetermined dose has been reached, the dose processor 170 closes the beam shutter 172 and terminates the process. During the accumulation of a predetermined dose, the articulation/rotation mechanism 204 can be used to manipulate the workpiece 160 to ensure that all desired surfaces are processed.

圖3係根據本發明的具體實例之中性束處理設備300的圖式,其使用靜電偏轉板來分離GCIB之帶電與未帶電部分。束線艙107圍住該電離器及加速器區域及該工件處理區域。該束線艙107具有高電導及如此該壓力係實質 上處處一致。真空泵146b抽空該束線艙107。氣體係以由噴射氣體118傳輸之團簇及未團簇的氣體形式及以漏過該氣體漏杓孔120之額外未團簇的氣體形式流入束線艙107中。壓力感應器330透過電纜332將來自束線艙107的壓力資料傳送至測量及顯示出在束線艙107中之壓力的壓力感應器控制器334。在束線艙107中的壓力依進入束線艙107中的氣流與真空泵146b的泵速度之差額而定。藉由選擇氣體漏杓孔120的直徑、通過噴嘴110的來源氣體112流及真空泵146b的泵速度,於束線艙107中之壓力係在藉由設計及藉由噴嘴流決定的壓力PB處平衡。該GCIB從接地電極144至工件座162的飛行路徑係例如100公分。藉由設計及調整,PB可係大約6x10-5托耳(8x10-3帕斯卡)。因此,壓力與束路徑長度之乘積係大約6x10-3托耳-公分(0.8帕斯卡-公分)及該束的氣體標靶厚度係每平方公分大約1.94x1014個氣體分子,此係結合了由於該氣體簇在電離器122中的初始離子化與在GCIB 128中之氣體簇離子間發生的碰撞之單體放出,且已觀察到在GCIB 128中的氣體簇離子有效解離及產生完全解離之經加速的中性束314。VAcc可例如係30千伏及該GCIB 128係藉由該電壓加速。繞著GCIB 128的軸154配置偏轉板對(302及304)。偏轉板電源供應器306經由電導線308將正偏轉電壓VD提供至偏轉板302。偏轉板304係藉由電導線312及通過電流感應器/顯示器310連接至接地。偏轉板電源供應器306可手動地控制。VD可從零調整至足以完全將GCIB 128的離子化部分316偏轉到偏轉板304 上之電壓(例如,幾千伏特)。當該GCIB 128的離子化部分316係偏轉到偏轉板304上時,所產生的電流ID流過電導線312及用於指示的電流感應器/顯示器310。當VD係零時,GCIB 128未經偏轉及行進至工件160及工件座162。收集在工件160及工件座162上的GCIB束電流IB及讓其流過電導線168及電流感應器/顯示器320至接地。IB係在電流感應器/顯示器320上指示出。束閘172係藉由束閘控制器336透過連桿組338控制。束閘控制器336可手動或可以電或機械限時一預設定值以打開該束閘172一段預定區間。在使用時,VD係設定為零,及測量攻擊該工件座的束電流IB。根據先前對所提供的GCIB製程配方之經驗,以所測量的電流IB為基準決定所提供的處理之初始照射時間。增加VD直到全部所測量的束電流從IB轉移至ID,及ID不再隨著VD增加而增加時。在此時,包含初始GCIB 128之高能量解離組分的中性束314照射工件座162。然後,關閉束閘172及藉由習知的工件負載工具(無顯示)將工件160放置到工件座162上。打開束閘172一段預定的初始輻射時間。在該照射區間後,如需要可檢查工件及調整處理時間以根據所測量的GCIB束電流IB來校正該中性束處理之想要的週期。在此校正方法後,可使用經校正的曝露週期來處理額外的工件。 3 is a diagram of a neutral beam processing apparatus 300 according to a specific example of the present invention, which uses an electrostatic deflection plate to separate the charged and uncharged parts of GCIB. The beam compartment 107 surrounds the ionizer and accelerator area and the workpiece processing area. The beam compartment 107 has high conductance and thus the pressure is substantially uniform everywhere. The vacuum pump 146b evacuates the beam compartment 107. The gas system flows into the beamline compartment 107 in the form of clustered and unclustered gas transported by the jet gas 118 and in the form of additional unclustered gas leaking through the gas leaking hole 120. The pressure sensor 330 transmits the pressure data from the wiring compartment 107 through the cable 332 to the pressure sensor controller 334 that measures and displays the pressure in the wiring compartment 107. The pressure in the beam compartment 107 depends on the difference between the airflow entering the beam compartment 107 and the pump speed of the vacuum pump 146b. By selecting the diameter of the gas skimmer aperture 120, the flow rate through the pump source 112 and pump 110 gas nozzles 146b, cabin pressure based on the beam line 107 of the flow determined by the pressure and by the design of the nozzle at P B balance. The flight path of the GCIB from the ground electrode 144 to the workpiece holder 162 is, for example, 100 cm. By design and adjustment, PB can be about 6x10 -5 Torr (8x10 -3 Pascal). Therefore, the product of pressure and beam path length is approximately 6x10 -3 Torr-cm (0.8 Pascal-cm) and the gas target thickness of the beam is approximately 1.94x10 14 gas molecules per square centimeter, which is due to the combination of the The initial ionization of the gas cluster in the ionizer 122 and the collision of the gas cluster ions in the GCIB 128 is released, and it has been observed that the gas cluster ions in the GCIB 128 effectively dissociate and produce a fully dissociated accelerated的的neutral beam 314. V Acc can be, for example, 30 kV and the GCIB 128 can be accelerated by the voltage. A pair of deflection plates (302 and 304) are arranged around the axis 154 of the GCIB 128. The deflection plate power supply 306 supplies the positive deflection voltage V D to the deflection plate 302 via the electric wire 308. The deflection plate 304 is connected to the ground through the electric wire 312 and through the current sensor/display 310. The deflection plate power supply 306 can be manually controlled. V D can be adjusted from zero to a voltage sufficient to completely deflect ionized portion 316 of GCIB 128 onto deflection plate 304 (eg, several thousand volts). When the GCIB 128 based ionizing portion 316 to deflect the deflecting plate 304, the generated current I D flowing through the conductor 312 and a current sensor for indicating / display 310. When V D is zero, GCIB 128 is not deflected and travels to workpiece 160 and workpiece holder 162. The GCIB beam current I B collected on the workpiece 160 and the workpiece holder 162 is allowed to flow through the electrical wire 168 and the current sensor/display 320 to ground. I B is indicated on the current sensor/display 320. The beam gate 172 is controlled by the beam gate controller 336 through the linkage group 338. The beam brake controller 336 may manually or electrically or mechanically limit a preset value to open the beam brake 172 for a predetermined interval. In use, the V D system is set to zero, and the beam current I B attacking the workpiece holder is measured. Based on the previous experience with the provided GCIB process recipe, the initial irradiation time of the provided treatment is determined based on the measured current IB . When V D is increased until all measured beam currents are transferred from I B to I D and I D no longer increases as V D increases. At this time, the neutral beam 314 containing the high-energy dissociation component of the initial GCIB 128 irradiates the workpiece holder 162. Then, the beam brake 172 is closed and the workpiece 160 is placed on the workpiece holder 162 by a conventional workpiece loading tool (not shown). The beam shutter 172 is opened for a predetermined initial irradiation time. After the irradiation interval, the workpiece can be inspected and the processing time adjusted if necessary to correct the desired cycle of the neutral beam processing based on the measured GCIB beam current IB . After this calibration method, the corrected exposure cycle can be used to process additional workpieces.

該中性束314包括該加速的GCIB 128之初始能量的可重覆分量。已經從該中性束314移除原始GCIB 128的殘餘離子化部分316及藉由接地的偏轉板304收集該部分。 從該中性束314移除的離子化部分316可包括單體離子及氣體簇離子,包括中尺度氣體簇離子。因為由於在離子化處理、束內碰撞、背景氣體碰撞及其它原因(此全部造成簇的磨蝕)期間的簇加熱之單體蒸發機制,該中性束實質上由中性單體組成,同時該分離的帶電顆粒占大多數為簇離子。本發明家已藉由合適的測量證實此,其包括再離子化該中性束及測量所產生的離子之電荷對質量比率。該經分離的帶電束組分大部分由中尺度簇離子和單體離子及或許某些大簇離子組成。如將在下列顯示出,藉由使用此中性束處理工件獲得某些優異的處理結果。 The neutral beam 314 includes a repeatable component of the initial energy of the accelerated GCIB 128. The residual ionized portion 316 of the original GCIB 128 has been removed from the neutral beam 314 and collected by the grounded deflection plate 304. The ionized portion 316 removed from the neutral beam 314 may include monomer ions and gas cluster ions, including mesoscale gas cluster ions. Because of the monomer evaporation mechanism of cluster heating during ionization treatment, intra-beam collision, background gas collision, and other reasons (which all cause cluster abrasion), the neutral beam is essentially composed of neutral monomers, while the The separated charged particles are mostly cluster ions. The inventors have confirmed this by suitable measurements, which include re-ionizing the neutral beam and measuring the charge-to-mass ratio of the generated ions. Most of this separated charged beam component is composed of mesoscale cluster ions and monomer ions and perhaps some large cluster ions. As will be shown below, some excellent processing results are obtained by using this neutral beam to process the workpiece.

圖4係根據本發明的具體實例之中性束處理設備400的圖式,其將熱感應器使用於中性束測量。熱感應器402經由低導熱度附件404接附至已接附至樞軸412的轉動式支撐臂410。致動器408經由可逆式旋轉動作416在該熱感應器402之截取中性束314或GCIB 128的位置與由414指示出之不截取任何束的停放位置間移動該熱感應器402。當熱感應器402係在停放位置(由414指示出)中時,該GCIB 128或中性束314繼續沿著路徑406照射工件160及/或工件座162。熱感應器控制器420控制熱感應器402的位置及進行由熱感應器402產生之信號處理。熱感應器402經由電纜418與熱感應器控制器420通聯。熱感應器控制器420經由電纜428與劑量測定控制器432通聯。束電流測量裝置424測量當GCIB 128攻擊工件160及/或工件座162時在電導線168中流動之束電流IB。束電流測量裝置424經由電纜426 將束電流測量信號通聯至劑量測定控制器432。劑量測定控制器432藉由經由連桿組434傳送的控制訊號來控制束閘172的打開及關閉狀態之設定。劑量測定控制器432經由電纜442控制偏轉板電源供應器440及可在零電壓與適當的正電壓間控制偏轉電壓VD,以將該GCIB 128的離子化部分316完全偏轉至偏轉板304。當GCIB 128的離子化部分316攻擊偏轉板304時,所產生的電流ID係藉由電流感應器422測量及經由電纜430與劑量測定控制器432通聯。在操作時,劑量測定控制器432將熱感應器402設定至停放位置414,打開束閘172,將VD設定至零,以便完整的GCIB 128攻擊工件座162及/或工件160。劑量測定控制器432記錄從束電流測量裝置424傳送的束電流IB。然後,劑量測定控制器432透過熱感應器控制器420所轉驛的命令將熱感應器402從停放位置414移動至截取GCIB 128。該熱感應器控制器420藉由計算來度量GCIB 128之束能量通量,其中該計算係以該感應器的熱容量及該熱感應器402當其溫度提高通過預定的測量溫度(例如,70℃)時所測量到之溫度提高速率為基礎;及將該經計算的束能量通量與劑量測定控制器432通聯,然後計算出如由熱感應器402測量出的束能量通量及由該束電流測量裝置424測量出的相應束電流之校正。然後,該劑量測定控制器432將熱感應器402停放在停放位置414處,允許其冷卻;及下命令對偏轉板302施加正VD,直到由於GCIB 128的離子化部分之全部電流ID皆轉移至偏轉板304。電流感應器422測量相應ID及讓其與劑 量測定控制器432通聯。該劑量測定控制器亦透過熱感應器控制器420所轉驛的命令將該熱感應器402從停放位置414移動至截取該中性束314。該熱感應器控制器420使用先前決定的校正因子及該熱感應器402當其溫度提高通過預定的測量溫度時之溫度提高速率來測量該中性束314的束能量通量,及將該中性束能量通量通聯至該劑量測定控制器432。該劑量測定控制器432計算出中性束分量,其中該分量係在感應器402處該中性束314能量通量的熱測量對完整的GCIB 128能量通量之熱測量的比率。在典型操作下,達成約5%至約95%的中性束分量。在開始處理前,該劑量測定控制器432亦測量電流ID,及決定在IB與ID之初始值間的電流比率。在處理期間,可使用即時ID測量乘以該初始IB/ID比率作為替代IB之連續測量,及在處理控制期間,由該劑量測定控制器432使用於劑量測定。因此,該劑量測定控制器432可補償在工件處理期間的任何束變動,僅如若可獲得完整的GCIB 128之實際束電流測量般。劑量測定控制器使用該中性束分量來計算用於特別的束處理之想要的處理時間。在處理期間,可根據用以校正在處理期間的任何束變動之經校正的ID測量來調整該處理時間。 4 is a diagram of a neutral beam processing apparatus 400 according to a specific example of the present invention, which uses a thermal sensor for neutral beam measurement. The thermal sensor 402 is attached to the rotating support arm 410 attached to the pivot 412 via the low thermal conductivity attachment 404. The actuator 408 moves the thermal sensor 402 via a reversible rotation action 416 between the position of the thermal sensor 402 that intercepts the neutral beam 314 or GCIB 128 and the parking position indicated by 414 that does not intercept any beam. When the thermal sensor 402 is in the parking position (indicated by 414), the GCIB 128 or neutral beam 314 continues to illuminate the workpiece 160 and/or the workpiece holder 162 along the path 406. The thermal sensor controller 420 controls the position of the thermal sensor 402 and performs signal processing generated by the thermal sensor 402. The thermal sensor 402 communicates with the thermal sensor controller 420 via a cable 418. The thermal sensor controller 420 communicates with the dosimetry controller 432 via a cable 428. The beam current measuring device 424 measures the beam current I B flowing in the electric wire 168 when the GCIB 128 attacks the workpiece 160 and/or the workpiece holder 162. The beam current measurement device 424 communicates the beam current measurement signal to the dosimetry controller 432 via the cable 426. The dosimetry controller 432 controls the setting of the opening and closing states of the beam gate 172 by the control signal transmitted through the link group 434. The dosimetry controller 432 controls the deflection plate power supply 440 via the cable 442 and can control the deflection voltage V D between zero voltage and an appropriate positive voltage to completely deflect the ionized portion 316 of the GCIB 128 to the deflection plate 304. When current I D based ionic moieties GCIB 128 316 304 attacks deflection plates, produced by the current sensor measurement 422 via a cable 430 and measuring the dose controller 432 Communications. In operation, the dosimetry controller 432 sets the thermal sensor 402 to the parking position 414, opens the beam gate 172, and sets V D to zero, so that the complete GCIB 128 attacks the workpiece holder 162 and/or the workpiece 160. The dosimetry controller 432 records the beam current I B transmitted from the beam current measuring device 424. Then, the dosimetry controller 432 moves the thermal sensor 402 from the parking position 414 to the intercepted GCIB 128 through the command transferred by the thermal sensor controller 420. The thermal sensor controller 420 measures the beam energy flux of the GCIB 128 by calculation, wherein the calculation is based on the thermal capacity of the sensor and the thermal sensor 402 when its temperature increases through a predetermined measurement temperature (for example, 70°C ) Based on the measured temperature increase rate; and communicating the calculated beam energy flux with the dosimetry controller 432, and then calculating the beam energy flux as measured by the thermal sensor 402 and the beam Correction of the corresponding beam current measured by the current measuring device 424. Then, the dosimetry controller 432 stops the thermal sensor 402 at the parking position 414 to allow it to cool; and commands to apply a positive V D to the deflection plate 302 until all the current I D due to the ionized portion of the GCIB 128 is reached移到转 describe板304. Measuring the corresponding current sensor 422 and let I D and dosimetry controller 432 Communications. The dosimetry controller also moves the thermal sensor 402 from the parking position 414 to intercept the neutral beam 314 through a command transferred by the thermal sensor controller 420. The thermal sensor controller 420 measures the beam energy flux of the neutral beam 314 using the previously determined correction factor and the temperature increase rate of the thermal sensor 402 when its temperature increases through a predetermined measurement temperature, and Sex beam energy flux is communicated to the dosimetry controller 432. The dosimetry controller 432 calculates the neutral beam component, where the component is the ratio of the thermal measurement of the energy flux of the neutral beam 314 at the sensor 402 to the thermal measurement of the complete GCIB 128 energy flux. Under typical operation, a neutral beam component of about 5% to about 95% is achieved. Before starting treatment, the dosimetry controller 432 also measure current I D, and determines the ratio between the current I B and the initial value of the I D. During the process, can be used for real time by multiplying the initial measurement I D I B / I D ratio as an alternative to the continuous measurement of I B, and during the control process, as determined by the controller 432 using the measured dose to dose. Therefore, the dosimetry controller 432 can compensate for any beam variations during workpiece processing, just as if a complete GCIB 128 actual beam current measurement is available. The dosimetry controller uses this neutral beam component to calculate the desired processing time for the particular beam processing. During processing, the processing time can be adjusted according to the measurement I D through any beam changes during the process for correcting the correction.

圖5係根據本發明的具體實例之中性束處理設備500的圖式,其使用在遏止偏轉板上所收集之經偏轉的離子束電流作為劑量測定方法之組分。簡單參照圖4,顯示在圖4中的劑量測定方法可遭遇到下列事實:電流ID包括 由於GCIB 128的離子化部分316之電流和產生自當該束的離子化部分316攻擊偏轉板304時發射噴出之二次電子的二次電子流。該二次電子產率可依在離子化部分316中的簇離子尺度分佈而變化。其亦可依偏轉板304的衝擊表面之表面狀態(瘕疵度等等)而變化。因此,在圖4所描述的方法中,ID之大小並非為由於GCIB 128的離子化部分316之電流的精確表示。現在再次參照圖5,可藉由在最接近接收離子化部分316之偏轉板304的表面處加入電子遏止柵電極502,在偏轉板304處實現GCIB 128的離子化部分316之經改良的測量。該電子遏止柵電極502對離子化部分316係高度透明,但是由第二遏止電源供應器506提供的第二遏止電壓VS2相對於偏轉板304係呈負偏壓。典型藉由級數係數十伏特的VS2達成有效遏止二次電子。藉由遏止二次電子發射,偏轉板電源供應器440的電流負載減低,及在GCIB 128的離子化部分316中,由ID表示的電流之精確度增加。電子遏止柵502係藉由絕緣支撐504與偏轉板304絕緣及維持在與其鄰近。 5 is a diagram of a neutral beam processing apparatus 500 according to a specific example of the present invention, which uses the deflected ion beam current collected on the containment deflection plate as a component of a dosimetry method. Simple Referring to FIG 4, a method for dosimetry in FIG. 4 may encounter the fact that: since when current I D comprising GCIB generating an ionization current 128 and 316, since when the portion of the beam portion 316 ionized attack deflector plate 304 The secondary electron flow that emits the ejected secondary electrons. The secondary electron yield may vary depending on the cluster ion size distribution in the ionization section 316. It can also vary depending on the surface condition (flaw, etc.) of the impact surface of the deflection plate 304. Thus, in the method described in FIG. 4, the size of I D is not accurately represented due to the GCIB ionization current portion 316 128. Referring now to FIG. 5 again, an improved measurement of the ionization portion 316 of the GCIB 128 can be achieved at the deflection plate 304 by adding an electron containment grid electrode 502 at the surface closest to the deflection plate 304 receiving the ionization portion 316. The electron suppression gate electrode 502 is highly transparent to the ionized portion 316 system, but the second suppression voltage V S2 provided by the second suppression power supply 506 is negatively biased with respect to the deflection plate 304 system. Typically, the effective suppression of secondary electrons is achieved by V S2 with a series coefficient of ten volts. Curb by secondary electron emission, the power supply current of the deflector plate 440 to reduce the load, and the ionized portion 316 GCIB 128, the accuracy of the current represented by I D increases. The electron containment grid 502 is insulated from and maintained adjacent to the deflector plate 304 by an insulating support 504.

圖6為根據本發明的具體實例之中性束處理設備550的圖式,其使用在法拉第杯中收集之經偏轉的離子束電流樣品作為劑量測定方法的組分。在本發明的此具體實例中,於法拉第杯558中捕獲該離子化部分316(如顯示在圖5中)的樣品556。在法拉第杯558中所收集的樣品電流IS經由電導線560傳導至電流感應器562進行測量,及該測量係經由電纜564與劑量測定控制器566通聯。法拉第杯558 提供優異的電流度量,其中該度量係藉由測量由偏轉板304(如顯示在圖5中)所收集的電流ID獲得。電流感應器562實質上如先前對電流感應器422(如顯示在圖5中)所描述般操作,除了電流感應器562已增加靈敏度以適應較小的IS量外,如與ID比較。劑量測定控制器566實質上如先前對劑量測定控制器432(如顯示在圖5中)所描述般進行操作,除了其經設計以適應較小的電流測量IS(如與圖5的ID比較)外。 6 is a diagram of a neutral beam processing apparatus 550 according to a specific example of the present invention, which uses a deflected ion beam current sample collected in a Faraday cup as a component of a dosimetry method. In this specific example of the invention, a sample 556 of the ionized portion 316 (as shown in FIG. 5) is captured in a Faraday cup 558. The sample current IS collected in the Faraday cup 558 is conducted to the current sensor 562 via the electric wire 560 for measurement, and the measurement is communicated with the dosimetry controller 566 via the cable 564. Faraday cup 558 provides excellent current metric, wherein the metric measuring system by a deflector plate 304 (as shown in FIG. 5) of the collected current I D is obtained. Current sensor 562 substantially as previously described for the current sensor 422 (as shown in FIG. 5) as described operations, in addition to the current sensor 562 has increased sensitivity to accommodate the external I S small amount, as compared with the I D. Dosimetry controller 566 substantially as previously described for the dosimetry controller 432 (as shown in FIG. 5) is operated as described, except that it is designed to accommodate a smaller measurement current I S (FIG. 5 as I D Compare) outside.

圖7係根據本發明的具體實例之中性束處理設備600的圖式,其經由該中性束314使用機械式掃瞄器602來掃描空間延伸的工件160,以使得該中性束容易均勻地掃描較大工件。因為該中性束314無法藉由磁性或靜電技術進行掃描,當欲處理的工件160係空間上大於中性束314之範圍及需要均勻的工件160處理時,使用機械式掃瞄器602經由中性束314來掃描工件160。機械式掃瞄器602具有一用以托住工件160的工件座616。將機械式掃瞄器602配置成該中性束314或GCIB 128可入射在工件160及/或工件座616上。當偏轉板(302,304)將離子化部分316偏轉出GCIB 128時,工件160及/或工件座616僅接收到中性束314。當偏轉板(302,304)不偏轉GCIB 128的離子化部分316時,該工件160及/或工件座616接收完整的GCIB 128。工件座616具導電性及藉由絕緣器614與接地絕緣。由GCIB 128入射在工件160及/或工件座616上的束電流(IB)經由電導線168傳導至束電流測量裝置424。束電流測量裝置424測量 IB及將該測量通聯至劑量測定控制器628。機械式掃瞄器602具有致動器基座604,其包括經由電纜620藉由機械式掃描控制器618控制的致動器。該機械式掃瞄器602具有能在Y方向610上可逆地動作的Y位移臺606;及具有能在X方向612上可逆地動作的X位移臺608,其中該X方向指為進及出圖7的紙平面。Y位移臺606及X位移臺608之移動係藉由在致動器基座604中的致動器於機械式掃描控制器618控制下驅動。機械式掃描控制器618經由電纜622與劑量測定控制器628通聯。該劑量測定控制器628的功能包括先前對劑量測定控制器432所描述的全部功能,與額外經由與機械式掃描控制器618通聯用以控制機械式掃瞄器602的功能。以所測量的中性束能量流通率為基準,劑量測定控制器628計算Y及X掃描速率及與機械式掃描控制器618通聯使得在工件160處理期間完成該工件160的整數完全掃描,保證該工件之完全及均勻的處理,及保證對工件160有預定的能量通量劑量。除了使用中性束及使用中性束能量流通率測量外,此掃描控制演算法習知及通常使用在例如習知GCIB處理工具及離子植入工具中。要注意的是,該中性束處理設備600可藉由控制該偏轉板(302,304)使得GCIB 128通過而沒有偏轉以允許完整的GCIB 128照射工件160及/或工件座616而使用作為習知GCIB處理工具。 7 is a diagram of a neutral beam processing apparatus 600 according to a specific example of the present invention, which uses a mechanical scanner 602 to scan a spatially extending workpiece 160 via the neutral beam 314 so that the neutral beam is easily uniform Scan larger workpieces. Because the neutral beam 314 cannot be scanned by magnetic or electrostatic technology, when the workpiece 160 to be processed is spatially larger than the neutral beam 314 and a uniform workpiece 160 is required for processing, the mechanical scanner 602 is used to pass through Sex beam 314 to scan the workpiece 160. The mechanical scanner 602 has a workpiece holder 616 for supporting the workpiece 160. The mechanical scanner 602 is configured such that the neutral beam 314 or GCIB 128 can be incident on the workpiece 160 and/or the workpiece holder 616. When the deflection plate (302, 304) deflects the ionized portion 316 out of the GCIB 128, the workpiece 160 and/or the workpiece holder 616 only receives the neutral beam 314. When the deflection plate (302, 304) does not deflect the ionized portion 316 of the GCIB 128, the workpiece 160 and/or the workpiece holder 616 receives the complete GCIB 128. The workpiece holder 616 is electrically conductive and insulated from the ground by an insulator 614. The beam current ( IB ) incident on the workpiece 160 and/or the workpiece holder 616 by the GCIB 128 is conducted to the beam current measuring device 424 via the electrical wire 168. The beam current measuring device 424 measures IB and communicates the measurement to the dosimetry controller 628. The mechanical scanner 602 has an actuator base 604 that includes an actuator controlled by a mechanical scanning controller 618 via a cable 620. The mechanical scanner 602 has a Y stage 606 that can reversibly move in the Y direction 610; and an X stage 608 that can reversibly move in the X direction 612, where the X direction refers to the incoming and outgoing images 7 paper plane. The movement of the Y stage 606 and the X stage 608 is driven by the actuator in the actuator base 604 under the control of the mechanical scan controller 618. The mechanical scanning controller 618 is in communication with the dosimetry controller 628 via a cable 622. The functions of the dosimetry controller 628 include all the functions previously described for the dosimetry controller 432, and the function of additionally controlling the mechanical scanner 602 via communication with the mechanical scanning controller 618. Based on the measured neutral beam energy flow rate, the dosimetry controller 628 calculates the Y and X scan rates and communicates with the mechanical scan controller 618 so that the integer full scan of the workpiece 160 is completed during the processing of the workpiece 160, ensuring that the Complete and uniform processing of the workpiece and ensure that the workpiece 160 has a predetermined energy flux dose. In addition to the use of neutral beams and the use of neutral beam energy flow rate measurements, this scan control algorithm is known and commonly used in, for example, conventional GCIB processing tools and ion implantation tools. It should be noted that the neutral beam processing apparatus 600 can be used as a habit by controlling the deflection plate (302, 304) to pass the GCIB 128 without deflection to allow the complete GCIB 128 to irradiate the workpiece 160 and/or the workpiece holder 616 Know GCIB processing tools.

圖8係根據本發明的具體實例之中性束處理設備700的圖式,其在束線艙107中提供有效的氣體壓力設定及控制。壓力感應器330經由電纜332將壓力測量資料從束線 艙107傳送至測量及顯示出在該束線艙中的壓力之壓力控制器716。在束線艙107中的壓力依進入束線艙107中的氣體流與真空泵146b的泵速度之差額而定。氣體瓶702包括束線氣體704,其較佳為與來源氣體112相同的氣體物種。該氣體瓶702具有可遠端操作的洩漏閥706及用以經由在束線艙107中的氣體擴散器710將束線氣體704洩漏進束線艙107中之氣體進料管708。該壓力控制器716能接收一輸入設定點(藉由手動引入或藉由從系統控制器(無顯示)自動引入),其中該設定點係呈壓力設定點、壓力乘以束路徑長度設定點(以預定的束路徑長度為基準)或氣體標靶厚度設定點形式。一旦已經對壓力控制器716建立設定點,其將調節進入該束線艙107中之束線氣體704流以在該中性束處理設備之操作期間維持該設定點。當使用此束線壓力調節系統時,該真空泵146b正常經估量,以便在缺乏將束線氣體704引進束線艙107中之下,於束線艙107中的基線壓力係低於想要的操作壓力。若該基線壓力經選擇,以便習知GCIB 128可傳播過該束路徑長度而沒有過多解離時,則該中性束處理設備700亦可使用作為習知GCIB處理工具。 FIG. 8 is a diagram of a neutral beam processing apparatus 700 according to a specific example of the present invention, which provides effective gas pressure setting and control in the beam cabin 107. The pressure sensor 330 transmits the pressure measurement data from the wire harness via the cable 332 The cabin 107 is transferred to a pressure controller 716 that measures and displays the pressure in the beam cabin. The pressure in the beam compartment 107 depends on the difference between the gas flow entering the beam compartment 107 and the pump speed of the vacuum pump 146b. The gas bottle 702 includes a beam gas 704, which is preferably the same gas species as the source gas 112. The gas bottle 702 has a remotely operable leak valve 706 and a gas feed pipe 708 to leak beam gas 704 into the beam cabin 107 via a gas diffuser 710 in the beam cabin 107. The pressure controller 716 can receive an input set point (by manual introduction or by automatic introduction from the system controller (no display)), where the set point is the pressure set point, the pressure multiplied by the beam path length set point ( Based on a predetermined beam path length) or a gas target thickness setpoint form. Once the setpoint has been established for the pressure controller 716, it will adjust the flow of beamline gas 704 into the beamline compartment 107 to maintain the setpoint during operation of the neutral beam processing apparatus. When using this beamline pressure regulation system, the vacuum pump 146b is normally estimated so that the baseline pressure in the beamline compartment 107 is lower than the desired operation without the introduction of the beamline gas 704 into the beamline compartment 107 pressure. If the baseline pressure is selected so that the conventional GCIB 128 can propagate through the beam path length without excessive dissociation, the neutral beam processing apparatus 700 can also be used as a conventional GCIB processing tool.

圖9係根據本發明的具體實例之中性束處理設備800的圖式,其使用靜電鏡來分離該帶電與中性束部分。將反射電極802與實質上透明的電網電極804配置成彼此錯位、彼此平行及與束軸154呈45度角。該反射電極802與實質上透明的電網電極804二者具有中心係在束軸154上的孔洞(各別為836及838),以准許該中性束314通過該二電極。 鏡子電源供應器810經由電導線806及808橫跨在反射電極802與實質上透明電網電極804間之間隙提供鏡子電壓VM,且其極性如在圖9中指示出般。VM經選擇係稍微大於VAcc+VR(VR係克服該噴射氣體簇在離子化及加速前所具有之熱能所需要的阻滯電位,VR的級數典型為幾千伏)。在該反射電極802與實質上透明的電網電極804間所產生之電場會相對於軸154偏轉該GCIB 128的離子化部分814大約90度角。配置法拉第杯812以收集GCIB 128的離子化部分814。遏止電極網柵電極816防止來自法拉第杯812的二次電子逃脫出。該遏止柵電極816係使用由第三遏止電源供應器822所提供的負第三遏止電壓VS3施加偏壓。VS3的級數典型為數十伏特。法拉第杯電流ID2代表在GCIB 128之經偏轉的離子化部分814中的電流(及因此在GCIB 128中的電流),其流過電導線820至電流感應器824。電流感應器824測量電流ID2及經由電導線826將該測量傳送至劑量測定控制器830。該劑量測定控制器830的功能係如先前對劑量測定控制器432所描述般,除了該劑量測定控制器830從電流感應器824接收ID2電流測量訊息及該劑量測定控制器830不控制偏轉板電源供應器440,反而是經由電纜840控制鏡子電源供應器810外。藉由將鏡子電源供應器810設定成輸出零伏特或VM,該劑量測定控制器830控制是將完整的GCIB 128或僅將GCIB 128的中性束314傳送至工件160及/或工件座616來進行測量及/或處理。 9 is a diagram of a neutral beam processing apparatus 800 according to a specific example of the present invention, which uses an electrostatic mirror to separate the charged and neutral beam portions. The reflective electrode 802 and the substantially transparent grid electrode 804 are configured to be offset from each other, parallel to each other, and at a 45-degree angle to the beam axis 154. Both the reflective electrode 802 and the substantially transparent grid electrode 804 have holes (836 and 838, respectively) centered on the beam axis 154 to allow the neutral beam 314 to pass through the two electrodes. The mirror power supply 810 provides the mirror voltage V M across the gap between the reflective electrode 802 and the substantially transparent grid electrode 804 via electrical leads 806 and 808, and its polarity is as indicated in FIG. 9. V M is selected to be slightly larger than V Acc +V R (V R is to overcome the blocking potential required by the thermal energy of the jet gas cluster before ionization and acceleration, and the series of V R is typically several thousand volts). The electric field generated between the reflective electrode 802 and the substantially transparent grid electrode 804 will deflect the ionized portion 814 of the GCIB 128 relative to the axis 154 by an angle of approximately 90 degrees. The Faraday cup 812 is configured to collect the ionized portion 814 of the GCIB 128. The containment electrode grid electrode 816 prevents secondary electrons from the Faraday cup 812 from escaping. The suppression gate electrode 816 is biased using the negative third suppression voltage V S3 provided by the third suppression power supply 822. The number of stages of V S3 is typically tens of volts. Faraday cup current representative current I D2 (and hence the current in the GCIB 128) in the ionization part 814 GCIB 128 in the deflected, it flows through the electrical leads 820 to the current sensor 824. The current sensor 824 measures the current ID2 and transmits the measurement to the dosimetry controller 830 via electrical leads 826. The function-based dosimetry controller 830 as the controller 432 described previously determined dose like, in addition to the dosimetry controller 830 receives the current I D2 dosimetry measurement message and the controller 830 from the current sensor 824 does not control the deflection plates Instead, the power supply 440 controls the mirror power supply 810 via the cable 840. By setting the mirror power supply 810 to output zero volts or V M , the dosimetry controller 830 controls whether to deliver the complete GCIB 128 or only the neutral beam 314 of the GCIB 128 to the workpiece 160 and/or the workpiece holder 616 To measure and/or process.

圖10係根據本發明的具體實例之中性束處理設 備940的圖式,其具有電離器122及工件160二者在接地電位下操作的優點。工件160係藉由導電工件座162保持在中性束314的路徑中,其依次由接附至低壓容器102壁的導電支撐成員954支撐。此外,工件座162及工件160係接地。加速電極948從電離器出口孔126引入氣體簇離子及透過由加速電源供應器944所提供的電壓電位VAcc加速該氣體簇離子以形成GCIB 128。電離器122的主體接地及VAcc係負極性。在噴射氣體118中之中性氣體原子具有級數係數十毫電子伏特的小能量。當它們凝結成簇時,此能量與簇尺度N呈比例地累積。足夠大的簇將從該凝結方法獲得不可忽略的能量,及當經由電壓電位VAcc加速時,每個離子的最後能量超過其中性簇噴射能量有VAcc。加速電極948的下游使用阻滯電極952,以保證GCIB 128的離子化部分958減速。阻滯電極952係由阻滯電壓電源供應器942在正阻滯電壓VR下施加偏壓。幾千伏的阻滯電壓VR通常適當,以保證在GCIB 128中的全部離子皆經減速及返回加速電極948。永久磁鐵陣列950附加至加速電極948以提供二次電子之磁性遏止,否則其將由於返回的離子攻擊該加速電極948而發射出。束閘172係一種機械式束閘及係設置在工件160的上游。劑量測定控制器946控制由該工件接收的處理劑量。在熱感應器控制器420控制下,將熱感應器402放進截取中性束314的位置用於中性束能量通量測量,或放至停放位置用於工件的中性束處理。當該熱感應器402係在束檢測位置時,測量該中性束能量通量及透過電纜956將 其傳送至劑量測定控制器946。在正常使用時,劑量測定控制器946關閉束閘172及命令熱感應器控制器420測量及報導該中性束314的能量通量。其次,習知的工件負載機制(無顯示)將新的工件放置在工件座上。以所測量的中性束能量通量為基準,該劑量測定控制器946計算照射時間用以提供預定想要的中性束能量劑量。該劑量測定控制器946命令熱感應器402離開中性束314及打開該束閘172一段該經計算的照射時間,然後在該經計算的照射時間結束時,關閉該束閘172以終止該工件160之處理。 10 is a diagram of a neutral beam processing apparatus 940 according to a specific example of the present invention, which has the advantage that both the ionizer 122 and the workpiece 160 operate at a ground potential. The workpiece 160 is held in the path of the neutral beam 314 by the conductive workpiece holder 162, which in turn is supported by the conductive support member 954 attached to the wall of the low-pressure vessel 102. In addition, the workpiece holder 162 and the workpiece 160 are grounded. The accelerating electrode 948 introduces gas cluster ions from the ionizer outlet hole 126 and accelerates the gas cluster ions through the voltage potential V Acc provided by the accelerating power supply 944 to form GCIB 128. The body of the ionizer 122 is grounded and V Acc is negative. The neutral gas atoms in the spray gas 118 have a small energy with an order coefficient of ten millielectron volts. When they condense into clusters, this energy accumulates in proportion to the cluster size N. A sufficiently large cluster will obtain non-negligible energy from this coagulation method, and when accelerated via the voltage potential V Acc , the final energy of each ion exceeds the neutral cluster ejection energy by V Acc . A blocking electrode 952 is used downstream of the acceleration electrode 948 to ensure that the ionized portion 958 of the GCIB 128 decelerates. Block 952 based electrode 942 at a positive bias is applied blocking voltage V R from the power supply voltage blocking. Blocking voltage of several thousand volts V R is generally appropriate to ensure that all ions in the GCIB 128 through a reduction in both the accelerating electrode 948 and the return. The permanent magnet array 950 is attached to the acceleration electrode 948 to provide magnetic containment of secondary electrons, otherwise it will be emitted due to the return ion attacking the acceleration electrode 948. The beam brake 172 is a mechanical beam brake and is arranged upstream of the workpiece 160. The dosimetry controller 946 controls the treatment dose received by the workpiece. Under the control of the thermal sensor controller 420, the thermal sensor 402 is placed in a position where the neutral beam 314 is intercepted for neutral beam energy flux measurement, or placed in a parking position for neutral beam processing of the workpiece. When the thermal sensor 402 is in the beam detection position, the energy flux of the neutral beam is measured and transmitted to the dosimetry controller 946 through the cable 956. In normal use, the dosimetry controller 946 closes the beam gate 172 and commands the thermal sensor controller 420 to measure and report the energy flux of the neutral beam 314. Secondly, the conventional workpiece loading mechanism (not shown) places new workpieces on the workpiece holder. Based on the measured neutral beam energy flux, the dosimetry controller 946 calculates the irradiation time to provide a predetermined desired neutral beam energy dose. The dosimetry controller 946 commands the thermal sensor 402 to leave the neutral beam 314 and open the beam gate 172 for the calculated irradiation time, and then at the end of the calculated irradiation time, close the beam gate 172 to terminate the workpiece 160 processing.

圖11係根據本發明的具體實例之中性束處理設備960的圖式,其中該電離器122在負電壓VR下操作及其中該工件在接地電位下操作。加速電極948從電離器出口孔126引出氣體簇離子及將該氣體簇離子朝向由加速電源供應器944所提供的電壓VAcc加速以形成GCIB 128。所產生的GCIB 128係藉由電壓VAcc-VR加速。接地電極962減速該GCIB 128的離子化部分958及讓其返回該加速電極948。 The system 11 in FIG. Specific examples of the present invention, the beam processing apparatus 960 in the drawings, the ionizer 122 wherein the workpiece is operated at ground potential a negative voltage V R and wherein the operation. The acceleration electrode 948 extracts gas cluster ions from the ionizer exit hole 126 and accelerates the gas cluster ions toward the voltage V Acc provided by the acceleration power supply 944 to form the GCIB 128. The generated GCIB 128 is accelerated by the voltage V Acc -V R. The ground electrode 962 decelerates the ionized portion 958 of the GCIB 128 and returns it to the acceleration electrode 948.

圖14係根據本發明的具體實例之中性束處理設備980的圖式。此具體實例係類似於在圖8中所顯示者,除了帶電束組分與中性束組分之分離係藉由磁場而非靜電場完成外。再次參照圖14,磁分析器982具有一由間隙分開的磁極面,其呈現出磁B-場。支撐984相對於該GCIB 128佈置磁分析器982,使得GCIB 128進入該磁分析器982的間隙,使得B-場的向量係與GCIB 128的軸154呈橫向。GCIB 128的離子化部分990係由磁分析器982偏轉。相對於該軸 154配置一具有中性束孔988的擋板986,以便該中性束314可通過該中性束孔988至工件160。GCIB 128的離子化部分990攻擊擋板986及/或低壓容器102壁,於此其解離成氣體而由真空泵146b抽掉。 14 is a diagram of a neutral beam processing apparatus 980 according to a specific example of the present invention. This specific example is similar to that shown in FIG. 8 except that the separation of the charged beam component and the neutral beam component is done by a magnetic field rather than an electrostatic field. Referring again to FIG. 14, the magnetic analyzer 982 has a magnetic pole face separated by a gap, which exhibits a magnetic B-field. The support 984 arranges the magnetic analyzer 982 relative to the GCIB 128 so that the GCIB 128 enters the gap of the magnetic analyzer 982 so that the vector system of the B-field is transverse to the axis 154 of the GCIB 128. The ionized portion 990 of the GCIB 128 is deflected by the magnetic analyzer 982. Relative to this axis 154 is configured with a baffle 986 having a neutral beam hole 988 so that the neutral beam 314 can pass through the neutral beam hole 988 to the workpiece 160. The ionized portion 990 of the GCIB 128 attacks the wall of the baffle 986 and/or the low-pressure container 102, where it dissociates into a gas and is drawn by the vacuum pump 146b.

圖12A至12D顯示出完整及經電荷分離的束在黃金薄膜上之比較性效應。在實驗設定中,藉由完整的GCIB(帶電與中性組分)、中性束(帶電組分已偏轉出該束)及僅包含帶電組分之偏轉束處理已沈積在矽基材上的黃金膜。全部三種狀況皆來自相同的初始GCIB,經30千伏加速的Ar GCIB。該束路徑在加速後之氣體標靶厚度為每平方公分大約2x1014個氬氣原子。對三種束各者來說,該曝露係與由完整的束(帶電加中性)在每平方公分2x1015個氣體簇離子之離子劑量下所攜帶的總能量相配。使用熱感應器來測量每種束的能量通量率及調整處理週期,以保證每個樣品接收到與完整的(帶電加中性)GCIB劑量之相同總熱能量劑量相等的劑量。 Figures 12A to 12D show the comparative effect of a complete and charge-separated beam on a gold film. In the experimental setup, the treatment of deposited on the silicon substrate by the complete GCIB (charged and neutral component), neutral beam (the charged component has been deflected out of the beam) and the deflected beam containing only the charged component Gold film. All three conditions are from the same initial GCIB, Ar GCIB accelerated at 30 kV. The thickness of the gas target after acceleration of the beam path is about 2×10 14 argon atoms per square centimeter. For each of the three beams, the exposure is matched to the total energy carried by the complete beam (charged plus neutral) at an ion dose of 2x10 15 gas cluster ions per square centimeter. A thermal sensor is used to measure the energy flux rate of each beam and adjust the processing cycle to ensure that each sample receives a dose equal to the total thermal energy dose of the full (charged plus neutral) GCIB dose.

圖12A顯示出具有平均粗糙度Ra大約2.22奈米的沈積態(as-deposited)黃金膜樣品之5微米乘以5微米原子顯微鏡(AFM)掃描圖及統計學分析。圖12B顯示出該黃金表面以完整的GCIB處理之AFM掃描圖,其平均粗糙度Ra已經減低至大約1.76奈米。圖12C顯示出僅使用該束的帶電組分(在從該中性束組分偏轉出後)處理之表面的AFM掃描圖,其平均粗糙度Ra已經增加至大約3.51奈米。圖12D顯示出僅使用該束的中性組分(在帶電組分已偏轉出該中性 束後)處理之表面的AFM掃描圖,其平均粗糙度Ra係平滑化至大約1.56奈米。經完整的GCIB處理之樣品(B)係比沈積態膜(A)平滑。經中性束處理的樣品(D)係比經完整的GCIB處理之樣品(B)平滑。以該束的帶電組分處理之樣品(C)實質上比沈積態膜粗糙。結果支持該束的中性部分促成平滑化及該束的帶電組分促成粗糙化之結論。 12A shows an as-deposited (as-deposited) of about 2.22 nm gold having an average roughness R a film sample of 5 microns by 5 microns atomic force microscope (AFM) scans and statistical analysis. FIG 12B shows the gold surface to complete an AFM scan GCIB processing of an average roughness R a has been reduced to about 1.76 nm. FIG 12C shows the use of only the charged components of the beam (in the post-deflection out of the neutral beam component) of the AFM scans the surface treatment of an average roughness R a has increased to about 3.51 nm. FIG. 12D shows an AFM scan of a surface treated with only the neutral component of the beam (after the charged component has been deflected out of the neutral beam), and its average roughness R a is smoothed to about 1.56 nm. The sample (B) after complete GCIB treatment is smoother than the as-deposited film (A). The neutral beam-treated sample (D) is smoother than the complete GCIB-treated sample (B). The sample (C) treated with the charged components of the beam is substantially rougher than the deposited film. The results support the conclusion that the neutral portion of the beam contributes to smoothing and the charged components of the beam contribute to roughening.

圖13A及13B顯示出使用來評估用於藥物溶析型冠狀動脈血管支架的藥物溶析速率之沈積在鈷-鉻試樣上的藥物膜,其進行完整的GCIB及中性束處理之比較結果。圖13A代表使用氬GCIB(包括帶電及中性組分),使用30千伏Vacc加速與每平方公分2x1015個氣體簇離子之照射劑量進行照射的樣品。圖13B代表使用來自氬GCIB,使用30千伏Vacc加速的中性束照射之樣品。該中性束係以相等於30千伏加速,每平方公分2x1015個氣體簇離子劑量(由束熱能量通量感應器決定的當量)之熱能量劑量照射。透過具有直徑大約50微米圓孔之陣列,允許束穿透的鈷鉻近距式遮罩對二者樣品進行照射。圖13A係以完整的束透過遮罩照射樣品的300微米乘以300微米區域之掃描式電子顯微圖。圖13B係以中性束透過遮罩照射樣品的300微米乘以300微米區域之掃描式電子顯微圖。顯示在圖13A中的樣品具有由通過遮罩的完整束所造成之損傷及蝕刻。顯示在圖13B中的樣品不具有可看見的效應。在生理鹽液溶液中的溶析速率測試中,經處理的樣品如圖B樣品(但是沒有遮罩)與經處理的樣品如圖13A樣品(但是沒有遮罩)比較具有優 異的(延遲)溶析速率。該結果支持以中性束處理促成想要的阻滯溶析效應,同時以完整的GCIB(帶電加中性組分)處理促成藥物因蝕刻的重量損失與較差(較少延遲)的溶析速率效應之結論。 Figures 13A and 13B show the comparison results of the complete GCIB and neutral beam treatment of the drug film deposited on the cobalt-chromium sample used to assess the rate of drug leaching for the drug leaching coronary stent. . FIG. 13A represents a sample irradiated with argon GCIB (including charged and neutral components), using 30 kV V acc acceleration and an irradiation dose of 2×10 15 gas cluster ions per square centimeter. Figure 13B represents a sample irradiated with a neutral beam accelerated from 30 kV V acc from argon GCIB. The neutral beam is irradiated with a thermal energy dose equal to 30 kV acceleration, 2x10 15 gas cluster ion doses per square centimeter (equivalent to the beam thermal energy flux sensor). Both arrays of cobalt-chromium close-up masks that allow beam penetration are illuminated through an array of circular holes with a diameter of approximately 50 microns. FIG. 13A is a scanning electron micrograph of a 300-micron by 300-micron area of a sample irradiated with a complete beam through a mask. FIG. 13B is a scanning electron micrograph of a 300-micron by 300-micron area of a sample irradiated with a neutral beam through a mask. The sample shown in FIG. 13A has damage and etching caused by the complete beam passing through the mask. The sample shown in Figure 13B has no visible effect. In the leaching rate test in physiological saline solution, the treated sample as shown in sample B (but without mask) has excellent (delayed) dissolution compared with the treated sample as shown in sample 13A (but without mask)析率。 Analysis rate. This result supports that neutral beam treatment contributes to the desired retarded leaching effect, while complete GCIB (charged plus neutral component) treatment contributes to drug weight loss due to etching and poor (less delayed) leaching rate The conclusion of the effect.

為了進一步闡明來自加速的GCIB之加速的中性束輔助藥物附著至表面及提供以此方式修改藥物而產生延遲的藥物溶析之能力,進行額外測試。從使用作為藥物沈積基材之高度拋光的乾淨半導體品質矽晶圓製備大約1公分乘以1公分(1平方公分)之矽試樣。藉由將500毫克的雷怕黴素(rapamycin)(目錄編號R-5000,LC Laboratories,Woburn,MA 01801,USA)溶解在20毫升丙酮中形成藥物雷怕黴素的溶液。然後,使用移液管將大約5微升小滴藥物溶液給料到每個試樣上。在該溶液之大氣蒸發及真空乾燥後,此於每個矽試樣上留下直徑大約5毫米的圓形雷怕黴素沈積物。將試樣分組及留下未照射(對照)或以多種中性束照射條件進行照射。然後,將該等組別放置在各別的人類血漿浴(每試樣一浴)中4.5小時,以允許藥物溶析進血漿中。在4.5小時後,從血漿浴中移出試樣,以去離子水沖洗及真空乾燥。在該處理中,於下列階段處進行重量測量:1)沈積前的乾淨矽試樣重量;2)在沈積及乾燥後,試樣加上沈積的藥物之重量;3)照射後重量;及4)血漿溶析及真空乾燥後重量。因此,可對每個試樣獲得下列資訊:1)沈積在每個試樣上之藥物負載的初始重量;2)在每個試樣的照射期間遺失之藥物重量;及3)在血漿溶析期間每個 試樣遺失的藥物重量。對每個照射的試樣來說,已確認在照射期間之藥物損失可忽略。在人類血漿中溶析期間的藥物損失係顯示在表1中。該等組別係如下:對照組別,無進行照射;組別1,以來自以30千伏Vacc加速的GCIB之中性束照射。組別1的照射束能量劑量係相等於以30千伏加速,每平方公分5x1014個氣體簇離子劑量(能量當量係由束熱能量通量感應器決定);組別2,以來自以30千伏VAcc加速的GCIB之中性束照射。組別2的照射束能量劑量係相等於以30千伏加速,每平方公分1x1014個氣體簇離子劑量(能量當量係由束熱能量通量感應器決定);及組別3,以來自以25千伏Vacc加速的GCIB之中性束照射。組別3的照射束能量劑量係相等於以25千伏加速,每平方公分5x1014個氣體簇離子劑量(能量當量係由束熱能量通量感應器決定)。 To further elucidate the ability of accelerated neutral beam-assisted drug attachment from accelerated GCIB to adhere to the surface and provide the ability to modify the drug in this manner to produce delayed drug leaching, additional testing was performed. A silicon sample of approximately 1 cm by 1 cm (1 cm 2) was prepared from a highly polished clean semiconductor quality silicon wafer used as a substrate for drug deposition. A solution of the drug rapamycin is formed by dissolving 500 mg of rapamycin (catalogue number R-5000, LC Laboratories, Woburn, MA 01801, USA) in 20 ml of acetone. Then, use a pipette to feed approximately 5 microliters of drug solution onto each sample. After atmospheric evaporation of the solution and vacuum drying, this left a circular deposit of rapamycin with a diameter of approximately 5 mm on each silicon sample. The samples were grouped and left unirradiated (control) or irradiated with various neutral beam irradiation conditions. The groups were then placed in separate human plasma baths (one bath per sample) for 4.5 hours to allow the drug to lyse into the plasma. After 4.5 hours, the sample was removed from the plasma bath, rinsed with deionized water and dried in vacuo. In this process, weight measurement is performed at the following stages: 1) the weight of the clean silicon sample before deposition; 2) the weight of the sample plus the deposited drug after deposition and drying; 3) the weight after irradiation; and 4 ) Weight after plasma lysis and vacuum drying. Therefore, the following information can be obtained for each sample: 1) the initial weight of the drug load deposited on each sample; 2) the weight of the drug lost during the irradiation of each sample; and 3) the plasma lysis The weight of the drug lost during each test period. For each sample irradiated, it was confirmed that the drug loss during the irradiation was negligible. The drug loss during lysis in human plasma is shown in Table 1. The groups are as follows: control group, no irradiation; group 1, irradiation with GCIB neutral beam from 30 kV V acc accelerated. The energy dose of the irradiation beam of group 1 is equivalent to acceleration at 30 kV, 5x10 14 gas cluster ion doses per square centimeter (energy equivalent is determined by the beam heat energy flux sensor); group 2, from 30 Neutral beam irradiation of GCIB accelerated by kilovolt V Acc . The energy dose of the irradiation beam of group 2 is equal to the acceleration of 30 kV, 1x10 14 gas cluster ion doses per square centimeter (the energy equivalent is determined by the beam heat energy flux sensor); and group 3 is from 25 kV V acc accelerated GCIB neutral beam irradiation. The energy dose of the irradiation beam of group 3 is equal to the acceleration of 25 kV, 5x10 14 gas cluster ion doses per square centimeter (the energy equivalent is determined by the beam thermal energy flux sensor).

Figure 105122882-A0202-12-0051-1
Figure 105122882-A0202-12-0051-1

表1顯示出對每個以中性束照射的情況(組別1至3)來說,在4.5小時溶析進人類血漿中期間之藥物遺失更低於未照射的對照組別。此指示出該中性束照射產生較好的藥物黏附力及/或減低溶析速率,如與未照射的藥物比較。p值(異質性未成對T檢定)指示出對每個經中性束照射的組別1至3來說,相對於對照組別,在人類血漿中溶析後之藥物滯留上的差異具統計顯著性。 Table 1 shows that for each case irradiated with a neutral beam (groups 1 to 3), the drug loss during the 4.5 hour leaching into human plasma was even lower than the unirradiated control group. This indicates that the neutral beam irradiation produces better drug adhesion and/or reduces the rate of leaching, as compared to unirradiated drugs. The p-value (heterogeneity unpaired T test) indicates that for each group 1-3 irradiated with neutral beams, the difference in drug retention after lysis in human plasma is statistically significant compared to the control group Significance.

圖15A至15C顯示出完整的束(帶電加上未帶電組分)與經電荷分離的束在如可典型使用於半導體應用中之單晶矽晶圓上的比較性效應。該矽基材具有大約1.3奈米之初始原始氧化層。在分別的例子中,該矽基材係使用完整的GCIB(帶電與中性組分)、來自GCIB的中性束(已藉由偏轉從該束移除帶電組分)、及僅包含GCIB在與中性組分分離後的帶電組分之帶電簇束處理。全部三種狀況皆來自相同的初始GCIB條件,從98%Ar與2%O2之混合物形成的經30千伏加速之GCIB。對三種束每種來說,該照射劑量係與由該完整的束(帶電加中性)在每平方公分2x1015個氣體簇離子之離子劑量下所攜帶的總能量相配。使用熱感應器來測量每種束的能量通量率及調整處理週期,以保證每個樣品接收與完整的(帶電加上中性)GCIB之相同總熱能量劑量相等的劑量。藉由切片接著藉由穿透式電子顯微鏡(TEM)成像來評估三個樣品。 15A to 15C show the comparative effect of a complete beam (charged plus uncharged components) and a charge-separated beam on a single crystal silicon wafer as it can be typically used in semiconductor applications. The silicon substrate has an initial original oxide layer of about 1.3 nanometers. In separate examples, the silicon substrate uses a complete GCIB (charged and neutral component), a neutral beam from GCIB (the charged component has been removed from the beam by deflection), and contains only GCIB in Charged cluster beam treatment of charged components after separation from neutral components. All three conditions are derived from the same initial GCIB conditions, a 30 kV accelerated GCIB formed from a mixture of 98% Ar and 2% O 2 . For each of the three beams, the irradiation dose matches the total energy carried by the complete beam (charged plus neutral) at an ion dose of 2×10 15 gas cluster ions per square centimeter. A thermal sensor is used to measure the energy flux rate of each beam and adjust the processing cycle to ensure that each sample receives a dose equal to the same total thermal energy dose of the full (charged plus neutral) GCIB. Three samples were evaluated by sectioning followed by transmission electron microscope (TEM) imaging.

圖15A係由完整的GCIB(帶電及中性束組分)照射之矽基材切片的TEM影像1000。該照射係從影像的頂端 朝向影像的底部之方向入射在矽基材上。在切片用於TEM成像前,該矽基材的頂端表面(照射表面)係塗佈以環氧樹脂外罩,以使得該切片操作容易及避免在切片過程期間損傷基材。在TEM影像1000中,可看見該環氧樹脂外罩1006係在影像頂端處。該照射形成包含矽及氧且具有最小厚度大約4.6奈米的非晶相區域1004。由於該照射處理,在非晶相區域1004與下面的單晶矽1002間形成具有波峰至波峰變化大約4.8奈米之粗糙界面1008。 FIG. 15A is a TEM image 1000 of a slice of a silicon substrate irradiated with complete GCIB (charged and neutral beam components). The irradiation is from the top of the image It is incident on the silicon substrate toward the bottom of the image. Before the slice is used for TEM imaging, the top surface (irradiated surface) of the silicon substrate is coated with an epoxy resin cover to make the slicing operation easy and avoid damaging the substrate during the slicing process. In the TEM image 1000, the epoxy resin cover 1006 can be seen at the top of the image. This irradiation forms an amorphous phase region 1004 containing silicon and oxygen and having a minimum thickness of about 4.6 nanometers. Due to this irradiation process, a rough interface 1008 having a peak-to-peak variation of about 4.8 nanometers is formed between the amorphous phase region 1004 and the underlying single crystal silicon 1002.

圖15B係由該GCIB之分離的帶電組分(僅有帶電部分)照射之矽基材切片的TEM影像1020。該照射係從影像頂端朝向影像底部的方向入射在矽基材上。在切片用於TEM成像前,該矽基材的頂端表面(照射表面)係塗佈以環氧樹脂外罩,以使得該切片操作容易及避免在切片過程期間損傷基材。在TEM影像1020中,可看見該環氧樹脂外罩1026係在影像頂端處。該照射形成包含矽及氧且具有最小厚度大約10.6奈米的非晶相區域1024。由於該照射處理,在該非晶相區域1024與下面的單晶矽1022間形成具有波峰至波峰變化大約5.9奈米之粗糙界面1028。 15B is a TEM image 1020 of a silicon substrate slice irradiated with the separated charged components (only charged parts) of the GCIB. The irradiation is incident on the silicon substrate from the top of the image toward the bottom of the image. Before the slice is used for TEM imaging, the top surface (irradiated surface) of the silicon substrate is coated with an epoxy resin cover to make the slicing operation easy and avoid damaging the substrate during the slicing process. In the TEM image 1020, the epoxy resin cover 1026 can be seen at the top of the image. This irradiation forms an amorphous phase region 1024 containing silicon and oxygen and having a minimum thickness of about 10.6 nm. Due to the irradiation process, a rough interface 1028 having a peak-to-peak variation of about 5.9 nm is formed between the amorphous phase region 1024 and the underlying single crystal silicon 1022.

圖15C係由中性部分(帶電組分係藉由偏轉分離及丟棄)照射之矽基材切片的TEM影像1040。該照射係從影像頂端朝向影像底部的方向入射在矽基材上。在切片用於TEM成像前,該矽基材之頂端表面(照射表面)係塗佈以環氧樹脂外罩,以使得該切片操作容易及避免在切片過程期間損傷基材。在TEM影像1040中,可看見該環氧樹脂外 罩1046係於影像頂端處。該照射形成包含矽及氧且具有實質上大約3.0奈米的均勻厚度之非晶相區域1044。由於該照射處理,在該非晶相區域1044與下面的單晶矽1042間形成具有原子等級之波峰至波峰變化的平滑界面1048。 FIG. 15C is a TEM image 1040 of a silicon substrate slice irradiated by a neutral portion (charged components are separated and discarded by deflection). The irradiation is incident on the silicon substrate from the top of the image toward the bottom of the image. Before slicing is used for TEM imaging, the top surface (irradiated surface) of the silicon substrate is coated with an epoxy resin cover to make the slicing operation easy and avoid damaging the substrate during the slicing process. In TEM image 1040, the epoxy resin can be seen outside The cover 1046 is attached to the top of the image. This irradiation forms an amorphous phase region 1044 including silicon and oxygen and having a uniform thickness of substantially about 3.0 nanometers. Due to the irradiation process, a smooth interface 1048 having a peak-to-peak variation of atomic order is formed between the amorphous phase region 1044 and the single crystal silicon 1042 below.

顯示在圖15A至15C中的處理結果指示出在半導體應用中,使用來自加速的GCIB藉由電荷分離之加速的中性束於經照射處理與未處理的區域間產生優異的界面,如與完整的GCIB或僅有GCIB的帶電部分比較。資料亦顯示出可在矽上使用來自GCIB之中性束形成平滑均勻的氧化物膜,及此膜無經常與使用習知GCIB相關的粗糙界面。不意欲由特別理論限制,咸信該改良可能產生自從該束消除中尺度簇或消除全部或大部分的簇。 The processing results shown in Figures 15A to 15C indicate that in semiconductor applications, the use of accelerated neutral beams from accelerated GCIB by charge separation produces an excellent interface between the irradiated and untreated areas, such as The GCIB or only the charged part of GCIB is compared. The data also shows that a neutral beam from GCIB can be used on silicon to form a smooth and uniform oxide film, and that this film does not have a rough interface often associated with the use of conventional GCIB. Without intending to be limited by a particular theory, Xianxin believes that this improvement may result from the elimination of mesoscale clusters or the elimination of all or most of the clusters from the beam.

圖16係一曲線圖1060,其顯示出在使用根據本發明的具體實例之中性束預形成的矽基材中,淺硼植入之二次離子質譜(SIMS)深度曲線測量的結果。該曲線圖標繪出以硼原子/立方公分(原子/立方公分)測量的硼濃度1062,如為以奈米測量的深度之函數。使用類似於顯示在圖4中的設備,從99%Ar與1%二硼烷(B2H6)之混合物形成經30千伏加速的GCIB。停滯艙壓力係80磅/平方英寸(5.5x105帕斯卡),噴嘴流係200標準立方公分/分鐘(3.3標準立方公分/秒)。完整的束電流(在藉由偏轉分離前之帶電加上中性組分)係大約0.55微安培(μA)。在束路徑中的壓力係維持在大約6.9x10-5托耳(9.2x10-3帕斯卡)及形成該壓力的背景氣體基本上係氬/二硼烷。在該加速器與工件間之區 域的氬/二硼烷氣體標靶厚度係大約2.23x1014氬/二硼烷氣體單體/平方公分,及該加速的中性束經觀察基本上由在標靶處完全解離的中性單體組成。使用靜電偏轉,全部帶電顆粒從該束軸偏轉開及偏轉出該束,形成基本上完全解離的中性束。因此,該中性束係一加速的單體中性氬/二硼烷束。使用熱感應器進行劑量測定以校正傳輸至矽基材的總中性束劑量,如此中性束所堆積的能量相等於由包括帶電及未帶電顆粒(沒有由電荷分離中和)二者之加速的(30千伏)GCIB由6.3x1014個氣體簇離子/平方公分照射劑量所堆積之能量。顯示在圖16中的深度曲線指示出產生自使用來自GCIB的中性束之中性束硼離子植入產生非常淺的硼植入。該接面深度係從濃度1018個硼原子/立方公分處估計,該深度發生在約12奈米深處,一非常淺的接面。在深度內的硼劑量積分指示出表面密度係大約7.94x1014個硼原子/平方公分。 FIG. 16 is a graph 1060 showing the results of secondary ion mass spectrometry (SIMS) depth curve measurement of shallow boron implantation in a silicon substrate preformed using a neutral beam according to a specific example of the present invention. The graph icon plots the boron concentration 1062 measured in boron atoms/cubic centimeters (atoms/cubic centimeters) as a function of depth measured in nanometers. Using equipment similar to that shown in Figure 4, a 30 kV accelerated GCIB was formed from a mixture of 99% Ar and 1% diborane (B 2 H 6 ). Stagnation pressure chamber lines 80 lbs / square inch (5.5x10 5 Pa), the nozzle flow line 200 standard cubic centimeters / minute (3.3 standard cubic centimeters / second). The complete beam current (charged before separation by deflection plus neutral component) is approximately 0.55 microamperes (μA). The pressure in the beam path is maintained at approximately 6.9x10 -5 Torr (9.2x10 -3 Pascal) and the background gas forming this pressure is essentially argon/diborane. The thickness of the argon/diborane gas target in the area between the accelerator and the workpiece is approximately 2.23× 10 14 argon/diborane gas monomer/cm 2, and the accelerated neutral beam is basically observed by the target The neutral monomer is completely dissociated. Using electrostatic deflection, all charged particles are deflected away from the beam axis and out of the beam, forming a neutral beam that is substantially completely dissociated. Therefore, the neutral beam is an accelerated single neutral argon/diborane beam. Dosimetry using a thermal sensor to correct the total neutral beam dose delivered to the silicon substrate so that the energy accumulated by the neutral beam is equal to the acceleration of both charged and uncharged particles (not neutralized by charge separation) (30 kV) GCIB is the energy accumulated by 6.3x10 14 gas cluster ions/cm2 irradiation dose. The depth curve shown in FIG. 16 indicates that the neutral beam boron ion implantation resulting from the use of the neutral beam from GCIB results in a very shallow boron implantation. The junction depth is estimated from a concentration of 10 18 boron atoms per cubic centimeter. The depth occurs at a depth of about 12 nm, a very shallow junction. The integration of the boron dose in the depth indicates that the surface density is approximately 7.94× 10 14 boron atoms/cm 2.

圖17係藉由來自GCIB的中性部分(帶電組分係藉由偏轉分離及丟棄)照射之矽基材切片的TEM影像1100。使用類似於顯示在圖4中的設備,從99%Ar與1%二硼烷(B2H6)的混合物形成之經30千伏加速的GCIB。停滯艙壓力係88磅/平方英寸(6.05x105帕斯卡),噴嘴流係200標準立方公分/分鐘(3.3標準立方公分/秒)。完整的束(在藉由偏轉分離前之帶電加中性組分)電流係大約0.55微安培(μA)。在該束路徑中的壓力維持在大約6.8x10-5托耳(9.07x10-3帕斯卡)及形成該壓力之背景氣體基本上係氬/二硼烷。因 此,在加速器出口孔與工件間之區域的氬/二硼烷氣體標靶厚度係大約2.2x1014氬/二硼烷氣體單體/平方公分,及已觀察到該加速的中性束在標靶處基本上由完全解離的中性單體組成。使用靜電偏轉,將全部帶電顆粒偏轉離開束軸及偏轉出該束軸而形成基本上完全解離的中性束。因此,該中性束係一加速的單體中性氬/二硼烷束。使用熱感應器進行劑量測定以校正傳輸至矽基材的總中性束劑量,如此該中性束所堆積的能量相等於由包括帶電及未帶電顆粒(沒有藉由電荷分離而中和)二者之經加速(30千伏)的GCIB由1.8x1014個氣體簇離子/平方公分照射劑量所堆積的能量。該照射係從影像頂端朝向影像底部的方向入射在矽基材上。在切片用於TEM成像前,該矽基材的頂端表面(照射表面)係塗佈以環氧樹脂外罩,以使得該切片操作容易及避免在切片過程期間損傷基材。再次參照圖17,在TEM影像1100中,可看見該環氧樹脂外罩1106係在該影像的頂端處。該照射形成一包含矽及硼且具有實質上大約1.9奈米的均勻厚度之非晶相區域1104。由於該照射處理,在非晶相區域1104與下面的單晶矽1102間形成具有原子等級之波峰至波峰變化的平滑界面1108。已知用以引進摻雜物、引發變形物種等等的先前技藝之半導體材料GCIB照射會在該經處理的膜與下面的基材間形成較粗糙的界面,類似於顯示在圖15A中之界面1008。已顯示出可使用二硼烷有效地對半導體摻雜硼,其在摻雜膜與下面的基材間具有高品質之界面。如與在該束中存在有中尺度簇離子之可產生 粗糙界面的習知GCIB技術比較,藉由使用包括其它摻雜物及/或晶格變形物種、用以增加摻雜物的固體溶解度極限之物種、或用以促進表面非晶相化的物種之其它氣體可獲得在膜與基材間具有優異界面之高品質膜。可單獨或以混合物使用來引進摻雜物的某些含摻雜物氣體之實施例有但非為限制二硼烷(B2H6)、三氟化硼(BF3)、膦(PH3)、五氟化磷(PF5)、胂(AsH3)及五氟化砷(AsF5),其可使用來將摻雜物原子併入氣體簇中。可單獨或以混合物使用來引進晶格變形物種的某些氣體有鍺烷(GeH4)、四氟化鍺(GeF4)、矽烷(SiH4)、四氟化矽(SiF4)、甲烷(CH4)。可單獨或以混合物使用來促進非晶相化之某些氣體有但非為限制氬(Ar)、鍺烷(GeH4)、四氟化鍺(GeF4)及氟(F2)。可單獨或以混合物使用來促進摻雜物溶解度的某些氣體有鍺烷(GeH4)及四氟化鍺(GeF4)。含摻雜物氣體、包括晶格變形物種的氣體、包含非晶相物種的氣體及/或包括用以改良摻雜物溶解度的物種之氣體(及選擇性惰性或其它氣體)可以混合物使用,以藉由該加速的中性束處理同步形成獲益組合。在圖17中,改變將數字指定符1108連接至其標的之導引線的顏色,以於該圖形中在具有不同背景的區域上維持對比。 Figure 17 is a TEM image 1100 of a silicon substrate slice irradiated with a neutral portion from GCIB (charged components are separated and discarded by deflection). Using an apparatus similar to that shown in Figure 4, a 30 kV accelerated GCIB formed from a mixture of 99% Ar and 1% diborane (B 2 H 6 ). The pressure in the stagnation chamber is 88 psi (6.05x10 5 Pascals), and the nozzle flow is 200 standard cubic centimeters per minute (3.3 standard cubic centimeters per second). The current of the complete beam (charged plus neutral component before separation by deflection) is about 0.55 microamperes (μA). The pressure in the beam path is maintained at approximately 6.8x10 -5 Torr (9.07x10 -3 Pascal) and the background gas forming this pressure is essentially argon/diborane. Therefore, the thickness of the argon/diborane gas target in the area between the accelerator exit hole and the workpiece is approximately 2.2× 10 14 argon/diborane gas monomer/cm 2, and the accelerated neutral beam has been observed in the standard The target is basically composed of completely dissociated neutral monomers. Using electrostatic deflection, all charged particles are deflected away from and away from the beam axis to form a substantially completely dissociated neutral beam. Therefore, the neutral beam is an accelerated single neutral argon/diborane beam. Dosimetry using a thermal sensor to correct the total neutral beam dose delivered to the silicon substrate, so that the energy accumulated by the neutral beam is equal to including charged and uncharged particles (no neutralization by charge separation) The accelerated (30 kV) GCIB is the energy accumulated by 1.8 x 10 14 gas cluster ions/cm 2 irradiation dose. The irradiation is incident on the silicon substrate from the top of the image toward the bottom of the image. Before the slice is used for TEM imaging, the top surface (irradiated surface) of the silicon substrate is coated with an epoxy resin cover to make the slicing operation easy and avoid damaging the substrate during the slicing process. Referring again to FIG. 17, in the TEM image 1100, the epoxy resin cover 1106 can be seen at the top of the image. The irradiation forms an amorphous phase region 1104 that includes silicon and boron and has a uniform thickness of substantially about 1.9 nanometers. Due to this irradiation process, a smooth interface 1108 having an atomic-level peak-to-peak change is formed between the amorphous phase region 1104 and the underlying single crystal silicon 1102. It is known that the irradiation of semiconductor material GCIB of the prior art used to introduce dopants, deformation-inducing species, etc. will form a rougher interface between the processed film and the underlying substrate, similar to the interface shown in FIG. 15A 1008. It has been shown that diborane can be used to effectively dope the semiconductor with boron, which has a high-quality interface between the doped film and the underlying substrate. If compared with the conventional GCIB technique that can produce rough interfaces with mesoscale cluster ions in the beam, by using other dopants and/or lattice deforming species, the solid solubility limit of the dopants is increased Species, or other gases used to promote the amorphous phase of the surface to obtain a high-quality film with an excellent interface between the film and the substrate. Some examples of dopant-containing gases that can be used alone or in a mixture to introduce dopants include, but are not limited to, diborane (B 2 H 6 ), boron trifluoride (BF 3 ), and phosphine (PH 3 ), phosphorus pentafluoride (PF 5 ), arsine (AsH 3 ) and arsenic pentafluoride (AsF 5 ), which can be used to incorporate dopant atoms into the gas cluster. Some gases that can be used alone or in mixtures to introduce lattice deforming species are germane (GeH 4 ), germanium tetrafluoride (GeF 4 ), silane (SiH 4 ), silicon tetrafluoride (SiF 4 ), methane ( CH 4 ). Some gases that can be used alone or in a mixture to promote amorphous phase include but are not limited to argon (Ar), germane (GeH 4 ), germanium tetrafluoride (GeF 4 ), and fluorine (F 2 ). Some gases that can be used alone or in mixtures to promote the solubility of dopants are germane (GeH 4 ) and germanium tetrafluoride (GeF 4 ). Dopant-containing gas, gas including lattice deformed species, gas containing amorphous phase species, and/or gas including species to improve the solubility of the dopant (and optionally inert or other gases) can be used in a mixture to The accelerated neutral beam processing synchronizes to form a benefit combination. In FIG. 17, the color of the guide wire connecting the number designator 1108 to its target is changed so as to maintain the contrast on the area with different backgrounds in the graph.

圖18闡明一深度曲線測量曲線圖1200,其係在使用來自GCIB之加速的中性束蝕刻於矽基材上之二氧化矽(SiO2)膜及蝕刻矽基材後獲得。使用類似於顯示在圖4中的設備,使用氬形成經30千伏加速的GCIB。停滯艙壓力 係28磅/平方英寸(1.93x105帕斯卡),噴嘴流係200標準立方公分/分鐘(3.3標準立方公分/秒)。完整的束(在藉由偏轉分離前之帶電加中性組分)電流係大約0.50微安培(μA)。在該加速器與工件間之區域的氬氣標靶厚度係大約1.49x1014個氬氣單體/平方公分,及已觀察到該加速的中性束在標靶處基本上由完全解離的中性單體組成。使用靜電偏轉,將全部帶電顆粒偏轉離開該束軸及偏轉出該束而形成中性束。因此,該中性束基本上係加速的中性氬單體束。使用熱感應器進行劑量測定以校正傳輸至矽基材的總中性束劑量,如此該中性束所堆積的能量相等於由包括帶電及未帶電顆粒(沒有由電荷分離中和)二者之經加速(30千伏)的GCIB由2.16x1016個氣體簇離子/平方公分照射劑量所堆積的能量。以窄的(大約0.7毫米寬)聚醯亞胺膜膠帶長條部分罩住在矽基材上的二氧化矽(SiO2)膜(大約0.5微米厚),然後以該加速的中性束照射。在照射後,移除該聚醯亞胺膠帶。再次參照圖18,使用TENCOR Alpha-Step 250輪廓儀,在沿著SiO2膜(於矽基材上)的表面及穿越由該聚醯亞胺膜膠帶罩住的區域之方向上測量由於產生自加速的中性束之蝕刻的步階曲線,以產生深度曲線測量曲線圖1200。高原區1202代表在聚醯亞胺膜下之未蝕刻的SiO2膜表面(在膜移除及清潔後),同時區域1204代表經蝕刻的部分。該加速的中性束產生大約2.4微米(μm)的蝕刻深度,其一路蝕刻穿越0.5微米SiO2膜及額外1.9微米進入在下面的結晶矽基材中而產生顯示於深度曲線測量曲線圖1200中之步階。 可使用氬及其它惰性氣體作為來源氣體,藉由物理方法進行蝕刻。藉由使用反應性來源氣體或使用併入反應性氣體的混合物來源氣體,亦可使用中性束來進行反應性蝕刻。可單獨或以含有惰性氣體之混合物使用的典型反應性氣體(非為限制)有氧(O2)、二氧化碳(CO2)、氮(N2)、氨(NH3)、氟(F2)、氯(Cl2)、六氟化硫(SF6)、四氟甲烷(CF4)、及其它可凝性含鹵素氣體。 FIG. 18 illustrates a depth curve measurement curve 1200 obtained after etching a silicon dioxide (SiO 2 ) film on a silicon substrate using an accelerated neutral beam from GCIB and etching the silicon substrate. Using an apparatus similar to that shown in Figure 4, argon was used to form a 30 kV accelerated GCIB. The stagnation chamber pressure is 28 pounds per square inch (1.93x10 5 Pascal), and the nozzle flow system is 200 standard cubic centimeters per minute (3.3 standard cubic centimeters per second). The current of the complete beam (charged plus neutral component before separation by deflection) is about 0.50 microamperes (μA). The thickness of the argon target in the area between the accelerator and the workpiece is approximately 1.49× 10 14 argon monomers per square centimeter, and it has been observed that the accelerated neutral beam at the target is substantially completely neutralized by dissociation Monomer composition. Using electrostatic deflection, all charged particles are deflected away from the beam axis and out of the beam to form a neutral beam. Therefore, the neutral beam is basically an accelerated neutral argon single beam. Dosimetry using a thermal sensor to correct the total neutral beam dose delivered to the silicon substrate, so that the energy accumulated by the neutral beam is equal to both charged and uncharged particles (not neutralized by charge separation) Accelerated (30 kV) GCIB energy is accumulated by 2.16x10 16 gas cluster ions/cm2 irradiation dose. Cover the silicon dioxide (SiO 2 ) film (approximately 0.5 microns thick) on the silicon substrate with a long strip of narrow (approximately 0.7 mm wide) polyimide film tape, and then irradiate with the accelerated neutral beam . After irradiation, the polyimide tape is removed. Referring again to FIG. 18, using the TENCOR Alpha-Step 250 profiler, the measurement was made in the direction along the surface of the SiO 2 film (on the silicon substrate) and across the area covered by the polyimide film tape. The step curve of the accelerated neutral beam etching to produce a depth curve measurement curve 1200. Plateau area 1202 represents the unetched SiO 2 film surface under the polyimide film (after film removal and cleaning), while area 1204 represents the etched portion. The accelerated neutral beam produces an etch depth of approximately 2.4 microns (μm), which is etched through a 0.5 micron SiO 2 film and an additional 1.9 microns into the underlying crystalline silicon substrate to produce the depth curve measurement graph 1200 Step. It is possible to use argon and other inert gases as the source gas and perform the etching by physical methods. By using a reactive source gas or using a mixture source gas that incorporates a reactive gas, a neutral beam can also be used for reactive etching. Typical reactive gases (not limited) that can be used alone or in mixtures containing inert gases are oxygen (O 2 ), carbon dioxide (CO 2 ), nitrogen (N 2 ), ammonia (NH 3 ), and fluorine (F 2 ) , Chlorine (Cl 2 ), sulfur hexafluoride (SF 6 ), tetrafluoromethane (CF 4 ), and other condensable halogen-containing gases.

圖19A及19B係TEM影像,其闡明藉由來自GCIBs之加速的中性束照射在結晶半導體材料中製造出非晶相層。在切片用於TEM成像前,每個樣品之頂端表面係塗佈以環氧樹脂外罩,以使得該切片操作容易及避免在切片過程期間損傷表面。當裸矽係曝露時,在空氣或水中自然地形成原始氧化物。 Figures 19A and 19B are TEM images illustrating the production of an amorphous phase layer in a crystalline semiconductor material by accelerated neutral beam irradiation from GCIBs. Before slicing for TEM imaging, the top surface of each sample was coated with an epoxy resin cover to make the slicing operation easy and avoid damaging the surface during the slicing process. When bare silicon is exposed, the original oxide naturally forms in the air or water.

圖19A係具有原始SiO2膜之矽基材切片的TEM影像1220。在該TEM影像1220中,可看見該環氧樹脂外罩1226係在影像頂端處。可在下面的矽基材1222上看見薄的(大約1.3奈米)原始氧化物膜1224。 FIG. 19A is a TEM image 1220 of a silicon substrate slice with original SiO 2 film. In the TEM image 1220, the epoxy resin cover 1226 can be seen at the top of the image. A thin (approximately 1.3 nm) original oxide film 1224 can be seen on the silicon substrate 1222 below.

圖19B係TEM影像1240,其顯示出藉由來自GCIB之加速的氬中性束照射矽基材之結果。在1%氫氟酸水溶液中清潔具有類似於顯示在圖19A中的原始氧化物膜之矽晶圓以移除原始氧化物。使用從氬形成、來自30千伏加速的GCIB之中性束(帶電組分係藉由偏轉從該束移除)照射該經清潔的矽基材。該照射劑量係使用熱感應器測量,其在能量上係與由完整的束(帶電加中性)在每平方公分 5x1014個氣體簇離子的離子劑量下所攜帶之總能量相配,由該中性束所堆積與完整的束之每平方公分5x1014個氣體簇離子的總能量相配。再次參照圖19B,TEM影像1240顯示出環氧樹脂外罩1246係在該結晶矽基材材料1242上面,藉由該加速的中性束照射於該矽表面中形成2.1奈米厚之非晶相膜1244。由於該照射處理,在非晶相膜1244與下面的結晶矽材料1242間形成具有波峰至波峰變化係原子等級之平滑界面1248。此顯示出可使用惰性氣體氬(Ar)在結晶半導體材料中形成非晶相層。使用來形成本發明的具體實例之加速的中性束且可使用來形成非晶相層之某些其它氣體(非為限制)包括氙(Xe)、鍺烷(GeH4)及四氟化鍺(GeF4)。此來源氣體可單獨或以含有氬或其它惰性氣體之混合物使用。在圖19B中,改變將數字指定符1248連接至其標的之導引線的顏色,以於該圖形中在具有不同背景的區域上維持對比。 FIG. 19B is a TEM image 1240 showing the results of irradiating the silicon substrate with an accelerated argon neutral beam from GCIB. The silicon wafer having the original oxide film similar to that shown in FIG. 19A is cleaned in a 1% hydrofluoric acid aqueous solution to remove the original oxide. The cleaned silicon substrate was irradiated with a GCIB neutral beam formed from argon and accelerated from 30 kV (charged components were removed from the beam by deflection). The radiation dose is measured using a thermal sensor, which is energy-matched to the total energy carried by the complete beam (charged plus neutral) at an ion dose of 5x10 14 gas cluster ions per cm2. The stacking of the sexual beams matches the total energy of 5x10 14 gas cluster ions per square centimeter of the complete beam. Referring again to FIG. 19B, the TEM image 1240 shows that the epoxy resin cover 1246 is on the crystalline silicon substrate material 1242, and the 2.1 nm thick amorphous phase film is formed on the silicon surface by the accelerated neutral beam irradiation 1244. Due to this irradiation process, a smooth interface 1248 having a peak-to-peak change atomic level is formed between the amorphous phase film 1244 and the underlying crystalline silicon material 1242. This shows that an inert gas argon (Ar) can be used to form an amorphous phase layer in a crystalline semiconductor material. Some other gases (not limited) that can be used to form an accelerated neutral beam of specific embodiments of the present invention and that can be used to form an amorphous phase layer include xenon (Xe), germane (GeH 4 ), and germanium tetrafluoride (GeF 4 ). This source gas can be used alone or in a mixture containing argon or other inert gas. In FIG. 19B, the color of the guide wire connecting the number designator 1248 to its target is changed so that the contrast is maintained on the area with a different background in the graph.

圖20A及20B係TEM影像,其闡明使用來自GCIBs之加速的中性束在矽上生長氧化物膜。在切片用於TEM成像前,每個樣品的頂端表面係塗佈以環氧樹脂外罩,以使得該切片操作容易及避免在切片過程期間損傷表面。 Figures 20A and 20B are TEM images illustrating the use of accelerated neutral beams from GCIBs to grow oxide films on silicon. Before slicing for TEM imaging, the top surface of each sample was coated with an epoxy resin cover to make the slicing operation easy and avoid damaging the surface during the slicing process.

圖20A係TEM影像1260,其顯示出藉由來自GCIB之加速的中性束照射矽基材之結果。在1%氫氟酸水溶液中清潔具有類似於顯示在圖19A中的原始氧化物膜之矽晶圓以移除原始氧化物。然後,使用從98%Ar與2%O2之 來源氣體混合物形成,來自30千伏加速的GCIB之中性束(帶電組分係藉由偏轉從該束移除)照射該經清潔的裸矽基材。該照射的中性束劑量高能量地相等(能量當量係由束熱能量通量感應器決定)於在每平方公分2.4x1013個氣體簇離子之離子劑量下之經30千伏加速的GCIB。再次參照圖20A,該TEM影像1260顯示出該環氧樹脂外罩1266係在該結晶矽基材材料1262上面,藉由該加速的中性束照射於矽表面中形成2奈米厚的氧化物膜1264。由於該照射處理,在氧化物膜1264與下面的結晶矽材料1262間形成具有波峰至波峰變化呈原子等級之平滑界面1268。在圖20A中,改變將數字指定符1268連接至其標的之導引線的顏色,以於圖形中在具有不同背景的區域上維持對比。 FIG. 20A is a TEM image 1260 showing the results of irradiating a silicon substrate with an accelerated neutral beam from GCIB. The silicon wafer having the original oxide film similar to that shown in FIG. 19A is cleaned in a 1% hydrofluoric acid aqueous solution to remove the original oxide. Then, using a source gas mixture formed from 98% Ar and 2% O 2 , a 30 kV accelerated GCIB neutral beam (charged components are removed from the beam by deflection) is irradiated to the cleaned bare silicon Substrate. The irradiated neutral beam doses are high-energy equal (energy equivalent is determined by the beam heat energy flux sensor) at 30 kV accelerated GCIB at an ion dose of 2.4×10 13 gas cluster ions per square centimeter. Referring again to FIG. 20A, the TEM image 1260 shows that the epoxy resin cover 1266 is on the crystalline silicon substrate material 1262, and the accelerated neutral beam is irradiated on the silicon surface to form a 2nm thick oxide film 1264. Due to this irradiation process, a smooth interface 1268 having a peak-to-peak change in atomic order is formed between the oxide film 1264 and the underlying crystalline silicon material 1262. In FIG. 20A, the color of the guide wire connecting the number designator 1268 to its target is changed to maintain contrast in areas with different backgrounds in the graphic.

圖20B係TEM影像1280,其顯示出藉由來自GCIB之加速的中性束照射矽基材之結果。在1%氫氟酸水溶液中清潔具有類似於顯示在圖19A中的原始氧化物膜之矽晶圓以移除原始氧化物。然後,使用從98%Ar與2%O2之來源氣體混合物形成,來自經30千伏加速的GCIB(帶電組分係藉由偏轉從該束移除)之中性束照射該經清潔的裸矽基材。該照射中性束劑量係高能量地相等(能量當量係由束熱能量通量感應器決定)於在每平方公分4.7x1014個氣體簇離子之離子劑量處之經30千伏加速的GCIB。再次參照圖20B,該TEM影像1280顯示出該環氧樹脂外罩1286係在該結晶矽基材材料1282上面,藉由加速的中性束照射於矽表面中形成3.3奈米厚之氧化物膜1284。由於該照射處 理,在氧化物膜1284與下面的結晶矽材料1282間形成具有波峰至波峰變化呈原子等級之平滑界面1288。此顯示出可使用包含氧的中性束在半導體材料之表面處形成氧化物層。所生長的膜厚度可藉由變化該照射劑量而改變。藉由在形成該加速的中性束時使用包含其它反應性物種之來源氣體,可在半導體或其它表面上生長其它型式膜,例如(非為限制)可單獨或呈含有氬(Ar)或其它惰性氣體之混合物使用氧(O2)、氮(N2)或氨(NH3)。在圖20B中,改變將數字指定符1288連接至其標的之導引線的顏色,以於圖形中在具有不同背景的區域上維持對比。 FIG. 20B is a TEM image 1280 showing the results of irradiating the silicon substrate with an accelerated neutral beam from GCIB. The silicon wafer having the original oxide film similar to that shown in FIG. 19A is cleaned in a 1% hydrofluoric acid aqueous solution to remove the original oxide. Then, using a source gas mixture formed from 98% Ar and 2% O 2 , a neutral beam from a 30 kV accelerated GCIB (charged components are removed from the beam by deflection) was used to irradiate the cleaned naked body Silicon substrate. The irradiation neutral beam dose is high-energy equal (energy equivalent is determined by the beam heat energy flux sensor) at 30 kV accelerated GCIB at an ion dose of 4.7 x 10 14 gas cluster ions per square centimeter. Referring again to FIG. 20B, the TEM image 1280 shows that the epoxy resin cover 1286 is on the crystalline silicon substrate material 1282, and an oxide film 1284 with a thickness of 3.3 nanometers is formed on the silicon surface by accelerated neutral beam irradiation. . Due to this irradiation process, a smooth interface 1288 having a peak-to-peak change in atomic order is formed between the oxide film 1284 and the underlying crystalline silicon material 1282. This shows that a neutral beam containing oxygen can be used to form an oxide layer at the surface of the semiconductor material. The thickness of the grown film can be changed by changing the irradiation dose. By using source gases containing other reactive species when forming the accelerated neutral beam, other types of films can be grown on semiconductors or other surfaces, such as (but not limited to) alone or as containing argon (Ar) or other Oxygen (O 2 ), nitrogen (N 2 ), or ammonia (NH 3 ) is used as the mixture of inert gases. In FIG. 20B, the color of the guide wire connecting the number designator 1288 to its target is changed to maintain contrast on areas with different backgrounds in the graphic.

圖21闡明一深度曲線測量曲線圖1300,其係在使用來自GCIB之加速的中性束於矽基材上沈積鑽石狀碳膜後獲得。使用類似於顯示在圖4中的設備,使用10%甲烷(CH4)與90%氬之來源氣體混合物形成經30千伏加速的GCIB。已觀察到該經加速的中性束在標靶處基本上由完全解離的中性單體組成。使用靜電偏轉,將全部帶電顆粒偏轉離開該束軸及偏轉出該束,形成中性甲烷/氬束。因此,該中性束基本上係經加速的中性甲烷/氬單體束。使用熱感應器進行劑量測定以校正傳輸至矽基材的總中性束,如此該中性束所堆積的能量相等於由包括帶電及未帶電顆粒(沒有由電荷分離中和)二者之加速(30千伏)的GCIB由2.8微安培氣體簇離子/平方公分照射劑量所堆積之能量。使用窄的(大約1毫米寬)長條狀聚醯亞胺膜膠帶部分罩住矽基材,然後,使用加速的中性束及遮罩照射該基材30 分鐘以沈積一鑽石狀碳膜。在照射後,移除該遮罩。再次參照圖21,使用TENCOR Alpha-Step 250輪廓儀,在沿著矽基材表面及穿越由該聚醯亞胺膜膠帶罩住的區域之方向上,測量由於產生自該加速的中性束之沈積物的步階曲線而產生深度曲線測量曲線圖1300。平坦區域1302代表在聚醯亞胺膜下之矽基材原始表面(在移除膜及清潔後),同時該區域1304代表沈積的鑽石狀碳部分。該加速的中性束產生大約2.2微米(μm)的沈積厚度,產生顯示在深度曲線測量曲線圖1300中之步階。對每個微安培/平方公分的GCIB電流(高能量當量,如由如在上述此段中提及的熱感應器決定)來說,該沈積速率係大約0.45奈米/秒。在其它測試中,於氬中之5%CH4混合物及7.5%混合物提供類似的結果,但是具有較低的沈積速率,此係產生自在來源氣體中較低的CH4百分比。氣體混合物及劑量之選擇准許可重覆沈積具有預定厚度的膜。CH4單獨或在含有氬或其它惰性氣體的混合物中係使用加速的中性單體束沈積碳之有效來源氣體。可單獨或以與惰性氣體之混合物使用且使用於加速的中性單體束之膜沈積的其它典型氣體(非為限制)有鍺烷(GeH4)、四氟化鍺(GeF4)、矽烷(SiH4)及四氟化矽(SiF4)。 FIG. 21 illustrates a depth curve measurement graph 1300 obtained after depositing a diamond-like carbon film on a silicon substrate using an accelerated neutral beam from GCIB. Using a similar display device in FIG. 4, using 10% methane (CH 4) and the source of 90% argon gas mixture to form a 30 kV acceleration GCIB. It has been observed that the accelerated neutral beam consists essentially of completely dissociated neutral monomer at the target. Using electrostatic deflection, all charged particles are deflected away from the beam axis and out of the beam, forming a neutral methane/argon beam. Therefore, the neutral beam is basically an accelerated neutral methane/argon monomer beam. Dosimetry using a thermal sensor to correct the total neutral beam transmitted to the silicon substrate, so that the energy accumulated by the neutral beam is equal to the acceleration of both charged and uncharged particles (not neutralized by charge separation) (30 kV) GCIB is the energy accumulated by the 2.8 microampere gas cluster ion/cm 2 irradiation dose. A narrow (approximately 1 mm wide) long polyimide film tape was used to partially cover the silicon substrate, and then the substrate was irradiated with an accelerated neutral beam and mask for 30 minutes to deposit a diamond-like carbon film. After irradiation, the mask is removed. Referring again to FIG. 21, using the TENCOR Alpha-Step 250 profiler, in the direction along the surface of the silicon substrate and across the area covered by the polyimide film tape, the neutral beam due to the acceleration is measured. The step curve of the sediment produces a depth curve measurement graph 1300. The flat area 1302 represents the original surface of the silicon substrate under the polyimide film (after film removal and cleaning), while the area 1304 represents the diamond-like carbon portion deposited. This accelerated neutral beam produces a deposited thickness of approximately 2.2 micrometers (μm), producing the steps shown in the depth curve measurement graph 1300. For each microampere/cm2 of GCIB current (high energy equivalent, as determined by the thermal sensor as mentioned in this paragraph above), the deposition rate is about 0.45 nm/sec. In other tests, the 5% CH 4 mixture and 7.5% mixture in argon provided similar results, but with a lower deposition rate, which resulted from a lower percentage of CH 4 in the source gas. The selection of gas mixture and dose permits repeated deposition of a film with a predetermined thickness. CH 4 alone or in a mixture containing argon or other inert gas is an effective source gas for carbon deposition using accelerated neutral monomer beams. Other typical gases (not limited) that can be used alone or in a mixture with an inert gas and used for accelerated neutral monomer beam film deposition are germane (GeH 4 ), germanium tetrafluoride (GeF 4 ), silane (SiH 4 ) and silicon tetrafluoride (SiF 4 ).

圖22顯示出產生自習知經清潔及拋光的硼矽酸鹽光學玻璃(Corning型式0211)樣品表面之500奈米乘以500奈米區域的原子顯微鏡(AFM)評估之典型映圖1320,其中該玻璃型式係通常使用在諸如光學窗、顯示器及/或觸控 式螢幕基材、顯微鏡玻片及蓋玻片、濾光器及其類似物之應用中。該表面具有平均粗糙度RA等於0.27奈米及存在有許多具有高度係幾個奈米級數的凸點1322。總波峰至波谷偏差級數係約4奈米或更多。 FIG. 22 shows a typical map 1320 generated from an atomic microscope (AFM) evaluation of a 500 nm by 500 nm area of a sample surface of a conventionally cleaned and polished borosilicate optical glass (Corning model 0211). Glass types are commonly used in applications such as optical windows, displays and/or touch screen substrates, microscope slides and coverslips, filters and the like. The surface has an average roughness R A equal to 0.27 nanometers and there are many bumps 1322 having a height series of several nanometers. The total peak-to-trough deviation series is about 4 nm or more.

使用來自加速的GCIB之基本上完全解離的中性束來處理此表面產生相當大地平滑及平坦化,及減低總波峰至波谷偏差。使用從氬來源氣體形成,來自30千伏加速的GCIB(帶電組分係藉由偏轉從該束移除)之中性束照射該習知經清潔及拋光的Corning型式0211光學玻璃樣品。該照射中性束劑量係高能量地相等(能量當量係藉由束熱能量通量感應器決定)於在每平方公分1x1014個氣體簇離子之離子劑量下之經30千伏加速的GCIB。 The use of a substantially completely dissociated neutral beam from accelerated GCIB to treat this surface produces a considerable smoothness and flattening, and reduces the total peak-to-trough deviation. A conventional cleaned and polished Corning-type 0211 optical glass sample was irradiated with a neutral beam of GCIB (charged components were removed from the beam by deflection) formed from an argon source gas, accelerated at 30 kV. The irradiation neutral beam dose is high-energy equal (energy equivalent is determined by the beam heat energy flux sensor) at 30 kV accelerated GCIB at an ion dose of 1×10 14 gas cluster ions per square centimeter.

圖23顯示出產生自經中性束照射的玻璃表面之500奈米乘以500奈米區域的AFM評估之映圖1340。該表面具有平均粗糙度RA等於0.13奈米,大約為未輻照的材料之粗糙度的一半。該表面基本上無凸點。總波峰至波谷偏差級數係約2奈米,大約為未輻照的光學表面之一半。 FIG. 23 shows a map 1340 of the AFM evaluation generated from the 500 nm by 500 nm area of the glass surface irradiated by the neutral beam. The surface has an average roughness R A equal to 0.13 nm, which is about half the roughness of the unirradiated material. The surface is substantially free of bumps. The total peak-to-trough deviation series is about 2 nm, which is about half of the unirradiated optical surface.

使用來自加速的GCIB藉由分離帶電組分與未帶電組分之加速的中性束顯示出能在半導體加工領域中有許多應用,其加入的利益為在藉由照射所形成的層與下面的半導體間之界面極為平滑及優於藉由習知GCIB照射所獲得的結果。 The use of accelerated GCIB from accelerated by separating charged and uncharged components of the accelerated neutral beam shows that it can have many applications in the field of semiconductor processing, and the added benefit is that the layer formed by irradiation and the underlying The interface between semiconductors is extremely smooth and superior to the results obtained by conventional GCIB irradiation.

另一種從GCIB或中性束處理獲益的光學應用係與將光學膜黏附到光學基材上之問題相關。光學裝置通常 藉由對其塗佈多種膜來進行改良以提高或改良性能。此光學膜可使用作為保護塗層、抗反射塗層、高反射塗層或其組合以製造出二向色膜濾光器。該塗層可係薄的金屬膜(例如,鋁或黃金)、介電質膜(例如,氟化鎂、氟化鈣或金屬氧化物)、或可係導電膜以提高抗靜電性質或提供作為用於顯示器或感觸式結構的電極。此薄膜塗層經常使用物理氣相沈積(PVD)技術或合適於該目的之其它習知技術沈積。常見的問題為此膜經常無法與基材或隨後的層形成強界面,因此同樣地會無法如想要般黏附。因為由PVD及其它習知技術施加之塗層經常因為其與基材材料的差異而無法對該基材材料形成強鍵結進而發生問題。可使用GCIB或中性束處理在光學基材上製造薄膜塗層(到光學裝置上或在其它光學塗層上),其比藉由習知技術施加之塗層具有更更強的黏附力。為了達成較高的黏附性能,可使用GCIB或中性束將初始種子塗層轉換成與基材強烈結合的界面層,然後在該界面層上形成最後塗層至想要的厚度。雖然可將GCIB及中性束二者使用於許多事件中,在該基材或塗層係介電質或低導電度材料的情況中,中性束因為前述提及的優點係較佳,其具有避免在離子束處理中由於固有的電荷傳輸之損傷。GCIB及中性束處理二者達成提高塗層的黏附力而沒有如使用習知單體離子束經常發生之明顯的次表面損傷。 Another optical application that benefits from GCIB or neutral beam processing is related to the problem of adhering optical films to optical substrates. Optical devices are usually It is improved by coating various films to improve or improve performance. This optical film can be used as a protective coating, anti-reflection coating, high-reflection coating, or a combination thereof to manufacture a dichroic film filter. The coating may be a thin metal film (for example, aluminum or gold), a dielectric film (for example, magnesium fluoride, calcium fluoride, or metal oxide), or a conductive film to improve antistatic properties or provide Electrodes for displays or tactile structures. This thin film coating is often deposited using physical vapor deposition (PVD) techniques or other conventional techniques suitable for this purpose. A common problem is that the film often fails to form a strong interface with the substrate or subsequent layers, and therefore likewise will not adhere as desired. Because coatings applied by PVD and other conventional techniques often fail to form strong bonds to the substrate material due to their differences from the substrate material, problems occur. Thin film coatings (on optical devices or on other optical coatings) can be made on optical substrates using GCIB or neutral beam processing, which has stronger adhesion than coatings applied by conventional techniques. In order to achieve higher adhesion performance, GCIB or neutral beam can be used to convert the initial seed coating into an interface layer strongly bonded to the substrate, and then form a final coating on the interface layer to the desired thickness. Although both GCIB and neutral beams can be used in many events, in the case where the substrate or coating is a dielectric or low-conductivity material, the neutral beam is better because of the aforementioned advantages, which It can avoid the damage caused by the inherent charge transfer in the ion beam treatment. Both GCIB and neutral beam treatment achieve improved adhesion of the coating without significant subsurface damage that often occurs with conventional monomer ion beams.

圖24A至24D係一圖式,其闡明在本發明的具體實例中使用GCIB或中性束技術於光學基材上形成強黏附 性光學塗層之步驟。圖24A係一圖式1400,其顯示出一具有非常薄的光學塗佈材料膜塗層1404之光學基材1402,其中該塗層已藉由習知技術諸如PVD預施加。在該光學塗佈材料1404與光學基材1402間有一具有習知的黏附性質(其可對意欲的應用不適當)之界面1406。該基材1402及光學塗佈材料1404的厚度不需呈比例地顯示出。GCIBs及中性束具有滲透特徵,其係與束來源材料、所使用的束加速電壓及存在於該束中的任何簇尺度範圍(雖然在經完全解離的中性束中不存在有簇)相依。例如,該解離的中性束可具有一進入典型光學塗佈材料中的滲透深度,其級數係約1至3奈米,同時包括簇的GCIB及中性束可具有級數係約2至20奈米之滲透深度(全部依塗佈材料及束參數而定)。在本發明的此具體實例之方法中,選擇該光學塗佈材料1404的厚度使得可實行的束典型參數將滲透該光學塗佈材料1404之整體厚度及亦滲透進該光學基材1402中一短距離(呈1至幾奈米的級數)。 24A to 24D are diagrams illustrating the use of GCIB or neutral beam technology to form strong adhesion on optical substrates in specific examples of the present invention. Steps for optical coatings. FIG. 24A is a diagram 1400 showing an optical substrate 1402 having a very thin optical coating material film coating 1404, where the coating has been pre-applied by conventional techniques such as PVD. There is an interface 1406 between the optical coating material 1404 and the optical substrate 1402 that has conventional adhesive properties (which may be inappropriate for the intended application). The thicknesses of the substrate 1402 and the optical coating material 1404 need not be proportionally shown. GCIBs and neutral beams have permeation characteristics, which are dependent on the beam source material, the beam acceleration voltage used, and any cluster-scale ranges present in the beam (although there are no clusters in the fully dissociated neutral beam) . For example, the dissociated neutral beam may have a penetration depth into a typical optical coating material with a series of about 1 to 3 nanometers, and the GCIB and cluster including clusters may have a series of about 2 to The penetration depth of 20nm (all depends on the coating material and beam parameters). In the method of this embodiment of the present invention, the thickness of the optical coating material 1404 is selected so that the typical parameters of the beam that can be implemented will penetrate the entire thickness of the optical coating material 1404 and also penetrate into the optical substrate 1402 for a short time. Distance (in the order of 1 to several nanometers).

圖24B係一圖式1410,其顯示出以係GCIB或中性束的束1412照射光學塗佈材料1404。與光學塗佈材料1404的厚度相關連進行該束1412特徵之選擇,以便保證入射在該光學塗佈材料1404上之束1412中的顆粒之至少一定分量完全滲透其。所滲透的那些通過習知界面1406及進入該光學基材1402中一段級數約1至幾奈米的距離。該照射的GCIB劑量或中性束劑量係例如每平方公分至少5x1013個離子,例如經30千伏加速的GCIB;或在中性束的情況 中,高能量地相等(能量當量係藉由束熱能量通量感應器決定)於例如具有每平方公分至少5x1013個氣體簇離子的離子劑量之經30千伏加速的GCIB。 24B is a diagram 1410 showing that the optical coating material 1404 is irradiated with a beam 1412 that is a GCIB or neutral beam. The characteristics of the beam 1412 are selected in relation to the thickness of the optical coating material 1404 in order to ensure that at least a certain component of the particles in the beam 1412 incident on the optical coating material 1404 fully penetrates it. Those penetrated pass through the conventional interface 1406 and enter the optical substrate 1402 at a distance of about 1 to several nanometers. The irradiated GCIB dose or neutral beam dose is, for example, at least 5x10 13 ions per square centimeter, such as GCIB accelerated at 30 kV; or in the case of a neutral beam, high energy is equal (energy equivalent is determined by the beam The thermal energy flux sensor is determined by, for example, a 30 kV accelerated GCIB with an ion dose of at least 5×10 13 gas cluster ions per square centimeter.

圖24C係一圖式1420,其顯示出產生自上述照射的結構。該束與光學塗佈材料1404薄膜之交互作用將原子從光學塗佈材料1404驅入光學基材1402中,形成一該光學塗佈材料1404與光學基材1402的原子親密混合之混合物區域1422,其中在該混合物區域的上區域中之光學塗佈材料原子的濃度梯度較高,及其在該混合物區域的下區域中係接近零。在該混合物區域1422的上區域中之類似原子使得與光學塗佈材料1404的原子強鍵結容易,造成該光學塗佈材料1404比在習知界面1406的情況中(顯示在圖4A中)更更強地黏附至該光學基材。該光學塗佈材料1404之厚度對想要的光學塗層性質來說會太薄,其中必需限制該厚度以允許該束滲透而形成該混合物區域1422,在此情況中,需要隨後沈積額外的光學塗佈材料以產生想要的光學塗層性質。 FIG. 24C is a diagram 1420 showing the structure resulting from the above irradiation. The interaction between the beam and the optical coating material 1404 film drives atoms from the optical coating material 1404 into the optical substrate 1402, forming a mixture region 1422 in which the optical coating material 1404 and the optical substrate 1402 atoms are intimately mixed. The concentration gradient of the optical coating material atoms in the upper region of the mixture region is higher, and it is close to zero in the lower region of the mixture region. Similar atoms in the upper region of the mixture region 1422 make strong bonding with atoms of the optical coating material 1404 easier, resulting in the optical coating material 1404 being more than in the case of the conventional interface 1406 (shown in FIG. 4A) Stronger adhesion to the optical substrate. The thickness of the optical coating material 1404 may be too thin for the desired optical coating properties, where the thickness must be limited to allow the beam to penetrate to form the mixture region 1422, in which case additional optical deposition is required subsequently The material is coated to produce the desired optical coating properties.

圖24D係一圖式1430,其闡明一額外沈積的光學塗佈材料層1432,以便光學塗佈材料1404加上光學塗佈材料1432的淨厚度增加至想要的光學效應所需要之厚度。材料1404與材料1432通常係相同的材料,然而它們可係不同材料,只要二種材料在其本身間形成強黏附力。在一種情況中,該材料1404可與該光學基材材料及上材料1432二者不同,但是該材料1404可經選擇以便與該基材及上材料 二者化學鍵結,然而該上材料及光學基材可彼此不具有固有的親和力。在二種材料(材料1404與材料1432)係相同的情況中,典型在二層間之原子類似性產生比習知界面1406(其顯示在圖24A中)所發生者更強的黏附力。 FIG. 24D is a diagram 1430 illustrating an additional deposited optical coating material layer 1432 so that the net thickness of the optical coating material 1404 plus the optical coating material 1432 increases to the thickness required for the desired optical effect. Material 1404 and material 1432 are usually the same material, but they can be different materials as long as the two materials form strong adhesion between themselves. In one case, the material 1404 may be different from both the optical base material and the upper material 1432, but the material 1404 may be selected to be different from the base material and the upper material The two are chemically bonded, however, the upper material and the optical substrate may not have an inherent affinity for each other. In the case where the two materials (material 1404 and material 1432) are the same, the atomic similarity between the two layers typically produces stronger adhesion than what occurs in the conventional interface 1406 (which is shown in FIG. 24A).

從GCIB或中性束處理獲益的進一步應用係與材料之大氣降解的問題相關。例如,光學及其它裝置通常使用具有高度想要的光學特徵之材料,但是其亦遭遇到具有當曝露至普通大氣條件時易受降解影響的特徵。當其實行上無法避免大氣曝露時,此限制其實用性或有用的服務壽命或有用的閑置壽命。此材料可由於表面氧化、大氣濕氣的吸收或由於該材料在大氣界面處的表面之其它反應而降解。特定的實施例有三硼酸鋰(LBO),LiB3O5材料,其係許多非線性光學(NLO)應用的較佳材料。在NLO應用中,LBO經常超過其它可獲得的材料,但是其遭遇到吸濕及藉由從環境或其它來源吸收濕氣而降解的缺點。此限制該材料在許多應用中的有效壽命,或甚至在其它應用中,該受限的大氣閑置壽命造成該材料於交付使用前降解。習知上,已使用添加型表面塗層藉由提供防潮物來減低濕氣吸收速率。但是,這些總是未如可需要般有效,及特別在光學功率密度高的應用(例如,雷射應用)之情況中,塗層可隨著時間剝離或其它方面降解及失效。如於此上述所描述,可藉由使用先前揭示出用以改良膜黏附力之GCIB及加速的中性束技術來改良此塗層的黏附力。但是,亦可使用GCIB或加速的中性束照射來形成一減低表面反應性及/ 或濕氣敏感性的薄阻礙物。若必要時,可使用該照射形成的阻礙物與隨後施加的習知阻礙塗層組合。雖然可在許多事件中使用GCIB及中性束二者,該經處理的材料係介電質或低導電度材料,該中性束因為前述提及的優點係較佳,其能避免在離子束處理時由於固有的電荷傳輸之損傷。LBO表面當直接曝露至典型週圍大氣條件時會快速損壞。加速的中性束照射LBO表面明顯延遲此損壞。 Further applications that benefit from GCIB or neutral beam processing are related to the problem of atmospheric degradation of materials. For example, optics and other devices often use materials with highly desirable optical characteristics, but they also encounter characteristics that are susceptible to degradation when exposed to ordinary atmospheric conditions. When its implementation cannot avoid atmospheric exposure, this limits its usefulness or useful service life or useful idle life. This material can be degraded due to surface oxidation, absorption of atmospheric moisture, or due to other reactions of the surface of the material at the atmospheric interface. Specific examples are lithium triborate (LBO), LiB 3 O 5 materials, which are preferred materials for many nonlinear optics (NLO) applications. In NLO applications, LBO often exceeds other available materials, but it suffers from the disadvantages of moisture absorption and degradation by absorbing moisture from the environment or other sources. This limits the effective life of the material in many applications, or even in other applications, the limited atmospheric idle life causes the material to degrade before being delivered for use. Conventionally, additive surface coatings have been used to reduce the rate of moisture absorption by providing moisture barriers. However, these are not always as effective as may be required, and particularly in the case of high optical power density applications (eg, laser applications), the coating may delaminate or otherwise degrade and fail over time. As described herein above, the adhesion of this coating can be improved by using the GCIB and accelerated neutral beam techniques previously disclosed to improve film adhesion. However, GCIB or accelerated neutral beam irradiation can also be used to form a thin barrier that reduces surface reactivity and/or moisture sensitivity. If necessary, the barrier formed by this irradiation may be used in combination with a conventional barrier coating applied subsequently. Although both GCIB and neutral beams can be used in many events, the treated material is a dielectric or low-conductivity material, and the neutral beam is better because of the aforementioned advantages, which can avoid the ion beam Damage due to inherent charge transfer during processing. The LBO surface will rapidly damage when directly exposed to typical surrounding atmospheric conditions. The accelerated neutral beam irradiation of the LBO surface significantly delays this damage.

圖25A及25B係未處理的LBO光學構件表面之原子力顯微圖映圖,其顯示出由於大氣曝露的降解。 Figures 25A and 25B are atomic force micrographs of the surface of untreated LBO optical components, showing degradation due to atmospheric exposure.

圖25A顯示出已經曝露至習知有空調的建築物之典型週圍實驗室環境(少於一小時)之未塗佈的LBO光學構件表面。該映圖顯示出該結晶之典型一微米乘以一微米平方區域。該線性溝槽狀外觀係殘餘在習知拋光表面上之刮傷。已顯露出許多昇高的凸塊,此係由於吸濕性LBO材料因大氣曝露開始表面降解的象徵。該表面具有平均粗糙度Ra大約0.30奈米。 Figure 25A shows the surface of an uncoated LBO optical member that has been exposed to a typical surrounding laboratory environment (less than one hour) of a conventional air-conditioned building. The map shows the typical one-micron by one-micron square area of the crystal. This linear groove-like appearance is a scratch that remains on the conventional polished surface. Many raised bumps have been revealed, which is a symbol of the surface degradation of the hygroscopic LBO material due to atmospheric exposure. The surface has an average roughness R a of about 0.30 nm.

圖25B顯示出相同的LBO材料片在曝露至相同的週圍實驗室環境100小時後之典型一微米乘以一微米平方區域。可看見該表面實質上已發展出降解,平均粗糙度Ra增加至大約3.58奈米,此係由於增加的面積及在表面上生長的凸塊高度。 Figure 25B shows the typical one micron times one micron squared area of the same piece of LBO material after being exposed to the same surrounding laboratory environment for 100 hours. The visible surface is substantially degraded been developed, to increase the average roughness R a of about 3.58 nm, this is due to increased area and bumps on the surface of the growing height.

圖26A及26B係使用來自GCIB之加速的中性束處理之LBO光學構件表面的原子力顯微圖映圖,其造成由於大氣曝露的降解減低。 Figures 26A and 26B are atomic force micrographs of the surface of LBO optical components treated with accelerated neutral beam treatment from GCIB, which results in reduced degradation due to atmospheric exposure.

圖26A顯示出與在上述圖25A中所顯示出者相同之未塗佈的LBO光學構件片表面。在短暫(少於一小時)曝露至習知有空調的建築物之週圍實驗室環境後,以加速的中性束照射處理該表面之一部分。在照射步驟後,測量顯示於圖26A中之照射部分的部分之原子顯微鏡影像。該映圖顯示出該結晶立即在照射後之照射部分的典型一微米乘以一微米平方區域。該線性溝槽狀刮傷不再明顯及該表面具有平均粗糙度Ra大約0.26奈米。該表面的照射部分係使用來自氬GCIB使用30千伏VAcc加速之中性束照射。該中性束係以每平方公分5x1018個氬原子的中性原子劑量照射。其它實驗已顯示出低如每平方公分2.5x1017個氬原子的中性原子劑量係有效(此外,有效的GCIB劑量具有類似的加速及簇離子尺度與劑量之組合,其提供類似的氬原子劑量)。 FIG. 26A shows the same surface of the uncoated LBO optical member sheet as shown in FIG. 25A described above. After a brief (less than one hour) exposure to the surrounding laboratory environment of a conventional air-conditioned building, a portion of the surface is treated with accelerated neutral beam irradiation. After the irradiation step, the atomic microscope image of the portion of the irradiated portion shown in FIG. 26A is measured. The map shows the typical one-micron by one-micron square area of the irradiated portion of the crystal immediately after irradiation. The linear groove-like scratches no longer apparent and that has an average surface roughness R a of about 0.26 nm. The irradiated part of the surface was irradiated with 30 kV V Acc accelerated neutral beam from argon GCIB. The neutral beam system is irradiated with a neutral atomic dose of 5× 10 18 argon atoms per square centimeter. Other experiments have shown that a neutral atomic dose as low as 2.5x10 17 argon atoms per square centimeter is effective (in addition, the effective GCIB dose has a similar acceleration and cluster ion scale and dose combination, which provides a similar argon atomic dose ).

圖26B顯示出在連續曝露至相同的週圍實驗室環境100小時後,相同LBO材料片的典型一微米乘以一微米平方區域。已發展出非常些微的表面降解,平均粗糙度Ra係大約0.29奈米。該中性束照射已產生淺表面修改,其功能如為濕氣吸收及或許其它降解形式的阻礙物,其延長該吸濕性LBO光學材料之功能性有用壽命。在100小時大氣曝露結束時,該照射表面顯露出與原始材料在僅一小時大氣曝露後相等或較好的品質。 Figure 26B shows a typical one-micron by one-micron square area of the same piece of LBO material after 100 hours of continuous exposure to the same surrounding laboratory environment. Has developed a very slight degradation of the surface, the average roughness R a of about 0.29 nm line. The neutral beam irradiation has produced shallow surface modifications, its function as an obstacle to moisture absorption and perhaps other forms of degradation, which extends the functional useful life of the hygroscopic LBO optical material. At the end of 100 hours of atmospheric exposure, the irradiated surface reveals the same or better quality as the original material after only one hour of atmospheric exposure.

從中性束處理獲益的進一步應用係與在矽基材上形成SiC或SiCx(0.05<X<3)層相關,其用以提供一較硬、 更耐熱、較少損傷傾向、更耐火性、具有改良的化學性質、具有不同晶格常數、可提供作為隨後層生長的基礎、可提供作為用於沈積隨後材料的基材表面(晶格相配或改良鍵結);提供作為在矽基材上的矽-碳化物半導體層或其它方面改良該矽基材。 Further applications that benefit from neutral beam processing are related to the formation of SiC or SiC x (0.05<X<3) layers on silicon substrates, which are used to provide a harder, more heat resistant, less prone to damage, and more fire resistant , With improved chemical properties, with different lattice constants, can be provided as a basis for subsequent layer growth, can be provided as a substrate surface for subsequent deposition of materials (lattice matching or improved bonding); provided as a silicon substrate The silicon-carbide semiconductor layer on top or other aspects improve the silicon substrate.

圖27A係一圖式1500,其顯示出一矽基材1502,其可係單晶矽基材及可具有如使用於半導體製造般的高純度。該矽基材1502的厚度不需呈比例地顯示出。該中性束具有的滲透特徵係與下列相依:束來源材料、所使用的束加速電壓、及存在於束中的任何簇尺度範圍(雖然在完全解離的中性束中不存在有簇)。例如,該解離的中性束可具有一進入典型光學塗佈材料中之滲透深度,其級數係約1至3奈米,同時包括簇的中性束可具有滲透深度級數係約2至20奈米(依標靶材料及束參數而定)。 FIG. 27A is a diagram 1500 showing a silicon substrate 1502, which can be a single crystal silicon substrate and can have high purity as used in semiconductor manufacturing. The thickness of the silicon substrate 1502 need not be proportionally shown. The penetration characteristics of this neutral beam are dependent on the following: the beam-derived material, the beam acceleration voltage used, and any cluster-scale range present in the beam (although there are no clusters in the completely dissociated neutral beam). For example, the dissociated neutral beam may have a penetration depth into a typical optical coating material with a series of about 1 to 3 nanometers, while the neutral beam including clusters may have a penetration depth of a series of about 2 to 20nm (depending on the target material and beam parameters).

圖27B係一圖式1510,其顯示出以係中性束(較佳為解離的中性束)之束1512照射該矽基材1502。選擇該束1512的特徵(包括加速電壓及劑量及來源氣體),以便其滲透該矽基材1502一預定想要的深度,以便其植入定量的碳原子而在植入區域中合適地製得每矽原子約0.05至約3個碳原子之C:Si比率。使用含碳來源氣體(較佳為甲烷)在該束中提供碳原子。該植入形成一具有想要的厚度及碳:矽原子比率之植入層(其可係非晶相)。該照射的中性束劑量及加速電壓之較佳範圍為例如從使用5至50千伏加速電壓所加速的氣體簇離子形成,在從該氣體簇離子形成中性 束或解離的中性束前,每平方公分約1x1014至約5x1016個碳原子(對包含中性甲烷簇及/或單體的束來說)。 FIG. 27B is a diagram 1510 showing that the silicon substrate 1502 is irradiated with a beam 1512 of a neutral beam (preferably a dissociated neutral beam). The characteristics of the beam 1512 (including accelerating voltage and dose and source gas) are selected so that it penetrates the silicon substrate 1502 to a predetermined desired depth so that it can be implanted with a fixed amount of carbon atoms to be properly prepared in the implanted area C:Si ratio of about 0.05 to about 3 carbon atoms per silicon atom. A carbon-containing source gas (preferably methane) is used to provide carbon atoms in the beam. The implantation forms an implantation layer (which may be an amorphous phase) with the desired thickness and carbon: silicon atomic ratio. The preferred range of the irradiated neutral beam dose and acceleration voltage is, for example, from the formation of gas cluster ions accelerated using an acceleration voltage of 5 to 50 kV before the formation of a neutral beam or dissociated neutral beam from the gas cluster ions , About 1x10 14 to about 5x10 16 carbon atoms per square centimeter (for bundles containing neutral methane clusters and/or monomers).

圖27C係一圖式1520,其顯示出產生自上述照射的結構。該束與矽基材1502的表面之交互作用將碳及氫原子植入該矽基材1502中形成植入層1522,於此碳原子與矽基材1502混合。來自該束的氫原子具揮發性及逃脫出該植入層,在該層中留下碳及矽原子。若該碳:矽比率係足夠高時,該植入層將由該碳原子打亂及可係非晶相。 FIG. 27C is a diagram 1520 showing the structure resulting from the above irradiation. The interaction between the beam and the surface of the silicon substrate 1502 implants carbon and hydrogen atoms into the silicon substrate 1502 to form an implant layer 1522, where the carbon atoms and the silicon substrate 1502 are mixed. The hydrogen atoms from the beam are volatile and escape the implanted layer, leaving carbon and silicon atoms in the layer. If the carbon:silicon ratio is sufficiently high, the implanted layer will be disrupted by the carbon atoms and may be an amorphous phase.

圖27D係一圖式1530,其闡明熱處理(退火)在該植入層1522上(圖27C)於熱處理步驟後之效應。該熱處理較佳為在氬環境或其它惰性環境中,使用能提供足夠的溫度-時間處理之爐或輻射加熱設備(根據已知技術)來退火該植入損傷及將植入的碳移至晶格替代位置。該經退火經熱處理層1532係恢復至實質上結晶形式。 FIG. 27D is a diagram 1530 illustrating the effect of heat treatment (annealing) on the implant layer 1522 (FIG. 27C) after the heat treatment step. The heat treatment is preferably in an argon environment or other inert environment, using a furnace or radiant heating device (according to known techniques) that provides sufficient temperature-time treatment to anneal the implant damage and move the implanted carbon to the crystal Grid replacement position. The annealed and heat-treated layer 1532 is restored to a substantially crystalline form.

從中性束處理獲益的進一步應用係與在矽基材上形成SiC或SiCx(0.05<X<3)層相關,如為可實行用於無光阻微影蝕刻的方法,如可應用在使用微影蝕刻來轉移圖案之矽裝置製造或使用其它材料及製程期間、應用在一藉由形成碳化物表面而硬化的裝置製造(特別是用於具有有限熱收支之微製造)期間。圖28A、28B、28C、28D、28E、28F及28G係圖式,其顯示出使用來自GCIB之加速的中性束在基材上形成硬遮罩圖案而沒有如某些裝置的先進微製造所需要般使用光阻之製程步驟。 Further applications that benefit from neutral beam processing are related to the formation of SiC or SiC x (0.05<X<3) layers on silicon substrates, such as methods that can be used for photoresist lithography etching, if applicable in During the fabrication of silicon devices that use lithography to transfer patterns or the use of other materials and processes, they are applied during the manufacture of devices hardened by forming carbide surfaces (especially for microfabrication with limited thermal budget). Figures 28A, 28B, 28C, 28D, 28E, 28F, and 28G are diagrams showing the use of accelerated neutral beams from GCIB to form a hard mask pattern on a substrate without advanced microfabrication facilities like some devices. The general process steps of using photoresist are required.

圖28A係一圖式1600,其顯示出(例如)矽基材 1602,其可係非晶相或單晶矽基材及可如係使用於半導體裝置製造或其它微製造般具高純度。該矽基材1602的厚度不需呈比例地顯示出。將接觸式樣板1604放置在矽基材1602上及與其接觸。在接觸式樣板1604中的開口攜帶一圖案,其想要從該基材1602之隨後的圖案化處理轉移至該基材1602。 FIG. 28A is a diagram 1600 showing (for example) a silicon substrate 1602, which can be an amorphous phase or a single crystal silicon substrate and can be of high purity as used in semiconductor device manufacturing or other microfabrication. The thickness of the silicon substrate 1602 need not be proportionally shown. The contact template 1604 is placed on and in contact with the silicon substrate 1602. The opening in the contact template 1604 carries a pattern that it wants to transfer to the substrate 1602 from the subsequent patterning process of the substrate 1602.

圖28B係一圖式1610,其顯示出以係中性束(較佳為解離的中性束)的束1612照射該矽基材1602。選擇該束1612的特徵(包括加速電壓及劑量及來源氣體),以便其通過在接觸式樣板1604中的開口而滲透該矽基材1602一段預定想要的深度,以便其植入定量的碳原子以在植入區域中合適地製得每矽原子約0.05至約3個碳原子(較佳為每矽原子約0.5至1.5個碳原子)之C:Si比率。使用含碳來源氣體(較佳為甲烷)在該束中提供碳原子。該植入在矽基材1602上於圖案化地區及/或區域1614中形成一具有想要的厚度(其可藉由預選擇該束之加速及劑量而控制在非常淺約1至約3奈米的範圍內)及想要的碳:矽原子比率之植入層(其可係非晶相)。該照射的中性束劑量及加速電壓之範圍係例如每平方公分約1x1014至約5x1016個碳原子(對包含中性甲烷簇及/或單體的束來說),其係在從一氣體簇離子形成中性束或解離的中性束前,使用5至50千伏加速電壓來加速該氣體簇離子形成。在矽基材1602上形成含碳圖案化地區及/或區域1614後,於額外處理前移除該接觸式樣板1604。可在形成該含碳圖案化地區及/或區域1614後, 選擇性熱處理該矽基材1602。該選擇性熱處理較佳為在氬環境或其它惰性環境中,使用能提供足夠的溫度-時間處理之爐或輻射加熱設備(根據已知技術)來退火在區域1614中之任何照射損傷及促進結晶性。 FIG. 28B is a diagram 1610 showing that the silicon substrate 1602 is irradiated with a beam 1612 of a neutral beam (preferably a dissociated neutral beam). The characteristics of the beam 1612 (including accelerating voltage and dose and source gas) are selected so that it penetrates the silicon substrate 1602 through the opening in the contact pattern 1604 to a predetermined desired depth so that it can implant a certain amount of carbon atoms A C:Si ratio of about 0.05 to about 3 carbon atoms per silicon atom (preferably about 0.5 to 1.5 carbon atoms per silicon atom) is suitably prepared in the implanted region. A carbon-containing source gas (preferably methane) is used to provide carbon atoms in the beam. The implant is formed on the silicon substrate 1602 in the patterned region and/or region 1614 to have a desired thickness (which can be controlled to be very shallow from about 1 to about 3 nanometers by preselecting the acceleration and dose of the beam In the range of meters) and the desired carbon: silicon atomic ratio of the implanted layer (which can be an amorphous phase). The range of the irradiated neutral beam dose and acceleration voltage is, for example, about 1x10 14 to about 5x10 16 carbon atoms per square centimeter (for beams containing neutral methane clusters and/or monomers), which ranges from Before the gas cluster ions form a neutral beam or a dissociated neutral beam, an acceleration voltage of 5 to 50 kV is used to accelerate the formation of the gas cluster ions. After the carbon-containing patterned regions and/or regions 1614 are formed on the silicon substrate 1602, the contact template 1604 is removed before additional processing. After forming the carbon-containing patterned regions and/or regions 1614, the silicon substrate 1602 may be selectively heat-treated. The selective heat treatment is preferably in an argon environment or other inert environment, using a furnace or radiant heating equipment (according to known techniques) that provides sufficient temperature-time treatment to anneal any irradiation damage and promote crystallization in the area 1614 Sex.

圖28C係一圖式1620,其顯示出另一種圖案樣板的安排。並非接觸式樣板,投影式樣板1622在以束1612照射矽基材1602期間係與矽基材1602間隔開。在束1612中的中性顆粒通過在樣板1622中之開口及照射該矽基材1602以形成植入地區及/或區域1614,於此其滲透過該矽基材1602一段預定想要的深度,以便其植入定量的碳原子以在植入區域中合適地製得每矽原子約0.05至約3個碳原子(較佳為每矽原子約0.5至1.5個碳原子)之C:Si比率。在矽基材1602上形成含碳圖案化地區及/或區域1614後,於額外處理前移除該投影式樣板1622。可在形成含碳圖案化地區及/或區域1614後,選擇性熱處理該矽基材1602。該選擇性熱處理較佳為在氬環境或其它惰性環境中,使用能提供足夠的溫度-時間處理之爐或輻射加熱設備(根據已知技術)來退火在區域1614中之任何照射損傷及促進結晶性。 FIG. 28C is a diagram 1620 showing another arrangement of pattern templates. Instead of a contact template, the projection template 1622 is spaced from the silicon substrate 1602 during irradiation of the silicon substrate 1602 with the beam 1612. The neutral particles in the beam 1612 pass through the opening in the template 1622 and irradiate the silicon substrate 1602 to form an implanted region and/or region 1614, where it penetrates through the silicon substrate 1602 to a predetermined desired depth, So that it implants a fixed amount of carbon atoms to properly prepare a C:Si ratio of about 0.05 to about 3 carbon atoms per silicon atom (preferably about 0.5 to 1.5 carbon atoms per silicon atom) in the implanted region. After the carbon-containing patterned regions and/or regions 1614 are formed on the silicon substrate 1602, the projection template 1622 is removed before additional processing. After forming the carbon-containing patterned regions and/or regions 1614, the silicon substrate 1602 may be selectively heat-treated. The selective heat treatment is preferably in an argon environment or other inert environment, using a furnace or radiant heating equipment (according to known techniques) that provides sufficient temperature-time treatment to anneal any irradiation damage and promote crystallization in the area 1614 Sex.

在如於圖28B或28C中闡明般形成含碳圖案化地區及或區域後,將其使用作為蝕刻遮罩來控制該基材之進一步加工。 After forming the carbon-containing patterned regions and/or regions as illustrated in FIG. 28B or 28C, it is used as an etching mask to control the further processing of the substrate.

圖28D係一圖式1530,其顯示出產生自在上述圖28B或28C中所闡明的圖案化結構之隨後處理。可使用第二束,較佳為中性束或解離的中性束1634來蝕刻基材表 面,包括地區及/或區域1614及未照射的表面二者。較硬及/或較緻密的地區及/或區域1614比未照射的表面更抗束蝕刻,及未照射的表面係比地區及/或區域1614優先地(更快速地)蝕刻。該束1634較佳為從氬GCIB形成且係在中和及分離前已經以10至70千伏加速之氬中性束或解離的中性束。此束對矽及SiC具有分別的蝕刻速率,其典型約10:1或20:1,依中性束能量及SiC品質而定。對30千伏加速來說,本發明家已測量16:1;及對50千伏加速來說,本發明家已測量約8:1(Si:SiCx蝕刻速率)。控制由束1634的蝕刻以在矽基材1602上產生溝槽1632,同時最低限度地蝕刻該較硬及/或較緻密的地區及/或區域1614,如在圖28D中闡明。雖然已經描述出使用氬中性束或解離的中性束蝕刻,要了解的是,可使用對Si:SiC具有適合的不同蝕刻速率之任何習知蝕刻方法來形成溝槽1632。 FIG. 28D is a diagram 1530 showing subsequent processing resulting from the patterned structure illustrated in FIG. 28B or 28C above. A second beam, preferably a neutral beam or a dissociated neutral beam 1634, can be used to etch the substrate surface, including both regions and/or regions 1614 and unirradiated surfaces. Harder and/or denser regions and/or regions 1614 are more resistant to beam etching than unirradiated surfaces, and unirradiated surfaces are etched preferentially (faster) than regions and/or regions 1614. The beam 1634 is preferably an argon neutral beam formed from GCIB of argon and has been accelerated at 10 to 70 kV or dissociated neutral beam before neutralization and separation. This beam has separate etch rates for silicon and SiC, which are typically about 10:1 or 20:1, depending on the neutral beam energy and SiC quality. For 30 kV acceleration, the inventor has measured 16:1; and for 50 kV acceleration, the inventor has measured about 8:1 (Si:SiC x etching rate). The etching by beam 1634 is controlled to create trenches 1632 in the silicon substrate 1602 while minimally etching the harder and/or denser regions and/or regions 1614, as illustrated in FIG. 28D. Although etching using argon neutral beams or dissociated neutral beams has been described, it is understood that the trench 1632 can be formed using any conventional etching method having a different etching rate suitable for Si:SiC.

圖28E係一圖式1640,其闡明另一種對在圖28D中所闡明者進行蝕刻的技術。在圖28E中,該蝕刻束1642經控制以便完全蝕刻掉該較硬及/或較緻密的地區及/或區域1614,留下高原區1644及溝槽1632,此二者具有由純基材1602材料組成的上表面。雖然已經描述出使用氬中性束或解離的中性束蝕刻,要了解的是,可使用對Si:SiC具有適合的不同蝕刻速率之任何習知蝕刻方法來形成溝槽1632。 FIG. 28E is a diagram 1640 illustrating another technique of etching the person illustrated in FIG. 28D. In FIG. 28E, the etching beam 1642 is controlled so as to completely etch away the harder and/or denser regions and/or regions 1614, leaving a plateau region 1644 and a trench 1632, both of which have a pure substrate 1602 The upper surface of the material. Although etching using argon neutral beams or dissociated neutral beams has been described, it is understood that the trench 1632 can be formed using any conventional etching method having a different etching rate suitable for Si:SiC.

圖28F係一圖式1650,其闡明在溝槽蝕刻後形成硬遮罩層之步驟。使用習知(較佳為低溫)方法,在基材 1602上形成硬遮罩(例如,二氧化矽)層1652,其係放置在高原區1644及溝槽1632上。想要但非基本的是,該硬遮罩層1652之厚度僅稍微比溝槽1632的深度厚。可使用非二氧化矽的其它材料,但需要其係非污染材料且將良好地執行作為用於隨後處理的硬遮罩。在氧化物形成後,使用習知方法諸如CMP(化學機械拋光)平坦化該基材表面。 FIG. 28F is a diagram 1650 illustrating the steps of forming a hard mask layer after trench etching. Use conventional (preferably low temperature) methods on the substrate A hard mask (eg, silicon dioxide) layer 1652 is formed on 1602, which is placed on the plateau region 1644 and the trench 1632. It is desirable, but not essential, that the thickness of the hard mask layer 1652 is only slightly thicker than the depth of the trench 1632. Other materials other than silicon dioxide can be used, but they need to be non-contaminating materials and will perform well as a hard mask for subsequent processing. After the oxide is formed, the substrate surface is planarized using conventional methods such as CMP (Chemical Mechanical Polishing).

圖28G係一圖式1660,其闡明在CMP平坦化後之組態。在表面平坦化組態中,該硬遮罩區域1664可與曝露出矽基材1602材料之地區1662交替。在某些狀況中,若想要昇高的矽高原區時,伴隨著曝露出矽用於隨後圖案化處理,此可係最後步驟。在其它製程中,可想要該上矽表面係與硬遮罩區域1664之底部共平面。在此情況中,需要額外的蝕刻。 FIG. 28G is a diagram 1660 illustrating the configuration after CMP planarization. In the surface planarization configuration, the hard mask region 1664 can alternate with the region 1662 where the silicon substrate 1602 material is exposed. In some cases, if you want to raise the silicon plateau area, it is the last step along with the exposure of silicon for subsequent patterning. In other processes, the upper silicon surface may be coplanar with the bottom of the hard mask region 1664. In this case, additional etching is required.

圖28H係一圖式1670,其闡明在額外蝕刻步驟後的組態。使用具有適合於蝕刻矽比氧化物快的不同蝕刻速率之習知蝕刻步驟。實施例有使用例如Cl2或CCl2F5或類似的電漿材料進行電漿蝕刻。藉由控制該蝕刻結束點與發生矽基材1602的上表面平坦化相重疊,將在硬遮罩1664的開口中之矽表面1672與矽基材1602的上表面製成平面,及獲得所闡明的組態。 FIG. 28H is a diagram 1670 illustrating the configuration after an additional etching step. A conventional etching step with different etching rates suitable for etching silicon faster than oxide is used. Examples include plasma etching using plasma materials such as Cl 2 or CCl 2 F 5 or the like. By controlling the end point of the etching to overlap with the planarization of the upper surface of the silicon substrate 1602, the silicon surface 1672 in the opening of the hard mask 1664 and the upper surface of the silicon substrate 1602 are made flat, and the clarification is obtained Configuration.

雖然已經相關於矽半導體材料描述出本發明的具體實例,要由發明家了解的是,其可相等地應用至其它半導體材料,包括鍺;及化合物半導體,包括但不限於III-V族及II-VI族及相關材料;及意欲本發明之範圍意欲包 括那些材料。要由發明家了解的是,雖然已經顯示出為了範例性目的,本發明之具體實例係對諸如使用矽半導體晶圓之平滑化、蝕刻、膜生長、膜沈積、非晶相及摻雜的製程有用,要由發明家了解的是,本發明的獲益並非僅限於在裸半導體表面上進行之處理,而且其對處理電路、電裝置、光學元件、積體電路、微電機械式系統(MEMS)裝置(及其部分)及通常使用習知現代技術在矽基材、其它半導體基材及其它材料的基材上建構之其它裝置部分亦相等地有用,及意欲本發明的範圍包括此應用。 Although specific examples of the present invention have been described in relation to silicon semiconductor materials, it is to be understood by the inventors that it can be equally applied to other semiconductor materials, including germanium; and compound semiconductors, including but not limited to III-V group and II -Group VI and related materials; and intended to include the scope of the present invention Include those materials. It should be understood by the inventors that although it has been shown for exemplary purposes, specific examples of the invention are processes such as smoothing, etching, film growth, film deposition, amorphous phase, and doping using silicon semiconductor wafers Useful, to be understood by the inventors is that the benefits of the present invention are not limited to processing on bare semiconductor surfaces, but also its processing circuits, electrical devices, optical components, integrated circuits, micro-electromechanical systems (MEMS ) Devices (and parts thereof) and other device parts commonly constructed on silicon substrates, other semiconductor substrates, and other material substrates using conventional modern technology are equally useful, and it is intended that the scope of the invention includes this application.

雖然已經關於處理多種電絕緣及/或非導電材料諸如絕緣藥物塗層、介電質膜諸如氧化物及氮化物、絕緣腐蝕抑制劑塗層、聚合物、有機膜、玻璃、陶瓷描述出將本發明之中性束施用於無電荷處理的獲益,要由發明家了解的是,全部差或低導電性的材料皆可從將於本文中所揭示出的中性束使用作為使用電荷轉移處理技術如離子束、電漿等等進行處理之代替技術而獲益,及意欲本發明的範圍包括此材料。要由發明家進一步了解的是,中性束處理的優點不僅因為其減低電荷特徵,而且亦有其用於處理許多導電材料,其中中性束處理特別是中性單體束處理的其它優點係其甚至在金屬及高導電材料中亦產生較少表面損傷、較好的平滑化及在處理與下面未處理區域間較平滑的界面。意欲本發明的範圍包括處理此材料。 Although it has been described regarding the treatment of various electrically insulating and/or non-conductive materials such as insulating drug coatings, dielectric films such as oxides and nitrides, insulating corrosion inhibitor coatings, polymers, organic films, glass, ceramics The benefits of applying the neutral beam to the chargeless treatment of the invention are to be understood by the inventor that all poor or low conductivity materials can be used from the neutral beam to be disclosed herein as the use of charge transfer treatment Technologies such as ion beams, plasmas, etc., benefit from alternative technologies for processing, and it is intended that the scope of the invention includes this material. It should be further understood by the inventor that the advantages of neutral beam processing are not only because of its reduced charge characteristics, but also that it is used to process many conductive materials, among which the other advantages of neutral beam processing, especially neutral monomer beam processing, are It produces less surface damage, better smoothing, and a smoother interface between the treated and untreated areas even in metals and highly conductive materials. It is intended that the scope of the invention includes the processing of this material.

雖然已經關於處理多種絕緣及/或非導電材料描述出將本文揭示出之中性束施用於無電荷處理的獲益,要 由發明家了解的是,無電荷中性束處理之獲益可相等地應用至以塗佈物或層形式或其它形式存在於絕緣層上面或配置在絕緣基材上之導電性、半導性或稍微導電材料的處理,其中該至少稍微導電材料不具有可信賴的接地連接或其它移除表面電荷的途徑,其中該電荷可藉由使用電荷轉移處理技術進行處理而引發。在此情況中,該至少稍微導電材料在處理期間帶電可對那些材料或下面的絕緣材料產生損傷。可藉由使用本發明的中性束處理來避免該帶電及損傷。發明家意欲本發明之範圍包括處理該至少稍微導電材料覆蓋一絕緣材料的此不同材料安排。 Although the benefits of applying the neutral beam disclosed in this article to chargeless processing have been described with regard to processing a variety of insulating and/or non-conductive materials, it is necessary to It is understood by the inventors that the benefits of no-charge neutral beam processing can be equally applied to the conductivity and semiconductivity that exist on the insulating layer in the form of a coating or layer or other forms or are arranged on an insulating substrate Or a slightly conductive material, where the at least slightly conductive material does not have a reliable ground connection or other means of removing surface charge, where the charge can be initiated by treatment using charge transfer processing techniques. In this case, the charging of the at least slightly conductive material during processing may cause damage to those materials or the underlying insulating material. The charging and damage can be avoided by using the neutral beam treatment of the present invention. The inventor intends that the scope of the present invention includes handling this different material arrangement of the at least slightly conductive material covering an insulating material.

雖然本發明已經以相關多個具體實例描述出,應該認知到本發明亦能在本發明的精神及範圍內包括廣泛多種進一步及其它具體實例。 Although the present invention has been described in terms of multiple specific examples, it should be recognized that the present invention can also include a wide variety of further and other specific examples within the spirit and scope of the present invention.

102‧‧‧低壓容器 102‧‧‧Low pressure container

104‧‧‧噴嘴艙 104‧‧‧ Nozzle compartment

107‧‧‧束線艙 107‧‧‧ Harness module

110‧‧‧噴嘴 110‧‧‧ nozzle

111‧‧‧氣體儲存圓筒 111‧‧‧Gas storage cylinder

112‧‧‧可凝性來源氣體 112‧‧‧Condensable source gas

113‧‧‧氣體計量供給閥 113‧‧‧Gas metering supply valve

114‧‧‧進料管 114‧‧‧ Feeding tube

116‧‧‧停滯艙 116‧‧‧Stall module

118‧‧‧超音波噴射氣體 118‧‧‧ Ultrasonic jet gas

120‧‧‧氣體漏杓孔 120‧‧‧Gas scoop hole

122‧‧‧電離器 122‧‧‧Ionizer

124‧‧‧白熾燈絲 124‧‧‧ Incandescent filament

126‧‧‧電離器出口孔 126‧‧‧Ionizer outlet

128‧‧‧GCIB 128‧‧‧GCIB

134‧‧‧陽極電源供應器 134‧‧‧Anode power supply

136‧‧‧燈絲電源供應器 136‧‧‧Filament power supply

138‧‧‧遏止電源供應器 138‧‧‧Stop power supply

140‧‧‧加速器電源供應器 140‧‧‧Accelerator power supply

142‧‧‧遏止電極 142‧‧‧Stop electrode

144‧‧‧接地電極 144‧‧‧Ground electrode

146a‧‧‧真空泵 146a‧‧‧Vacuum pump

146b‧‧‧真空泵 146b‧‧‧Vacuum pump

154‧‧‧軸 154‧‧‧axis

160‧‧‧工件 160‧‧‧Workpiece

162‧‧‧工件座 162‧‧‧Workpiece seat

164‧‧‧電絕緣器 164‧‧‧Electrical insulator

168‧‧‧電導線 168‧‧‧Electrical wire

172‧‧‧束閘 172‧‧‧ beam brake

300‧‧‧中性束處理設備 300‧‧‧Neutral beam processing equipment

302‧‧‧偏轉板 302‧‧‧Deflector

304‧‧‧偏轉板 304‧‧‧deflection plate

306‧‧‧偏轉板電源供應器 306‧‧‧Deflector power supply

308‧‧‧電導線 308‧‧‧Electrical wire

310‧‧‧電流感應器/顯示器 310‧‧‧current sensor/display

312‧‧‧電導線 312‧‧‧Electrical wire

314‧‧‧加速的中性束 314‧‧‧Accelerated neutral beam

316‧‧‧離子化部分 316‧‧‧Ionized part

320‧‧‧電流感應器/顯示器 320‧‧‧current sensor/display

330‧‧‧壓力感應器 330‧‧‧ pressure sensor

332‧‧‧電纜 332‧‧‧Cable

334‧‧‧壓力感應器控制器 334‧‧‧ pressure sensor controller

336‧‧‧束閘控制器 336‧‧‧ beam brake controller

338‧‧‧連桿組 338‧‧‧Link

VA‧‧‧陽極電壓 V A ‧‧‧Anode voltage

Vf‧‧‧燈絲電壓 V f ‧‧‧ filament voltage

VS‧‧‧遏止電壓 V S ‧‧‧ Suppression voltage

VAcc‧‧‧加速電壓 V Acc ‧‧‧ acceleration voltage

VD‧‧‧正偏轉電壓 V D ‧‧‧ Positive deflection voltage

ID‧‧‧電流 I D ‧‧‧ current

IB‧‧‧GCIB束電流 I B ‧‧‧GCIB beam current

Claims (20)

一種在基材表面上形成圖案化硬遮罩之無光阻方法,其包括下列步驟:提供一減壓艙;在該減壓艙內形成一包含氣體簇離子的氣體簇離子束,其中該氣體簇離子含有碳原子;在該減壓艙內加速該氣體簇離子以沿著束路徑形成一加速的氣體簇離子束;沿著該束路徑促進該加速的氣體簇離子之至少一部分碎裂及/或解離;從該束路徑移除帶電顆粒,以在該減壓艙中沿著該束路徑形成加速的中性束;將一圖案化樣板及該基材引進該減壓艙中;將該基材保持在該束路徑中;使用該加速的中性束,透過該圖案化樣板之開口照射該基材表面的一部分對其進行處理,以便藉由將碳原子植入該表面的照射部分而在該表面的照射部分上形成一硬化及/或緻密化的含碳圖案化層;分開該樣板與基材;第一次蝕刻該具有含碳圖案化層的表面,以優先地移除該表面之不含碳部分的材料,而形成一或多個溝槽及一或多個高原區;在該高原區及溝槽上形成一硬遮罩層; 平坦化該硬遮罩層以將其從高原區而非溝槽中移除;及選擇性使用該硬遮罩層作為遮罩進行該表面的第二次蝕刻,以移除基材材料。 A photoresist-free method for forming a patterned hard mask on a substrate surface includes the following steps: providing a decompression chamber; forming a gas cluster ion beam containing gas cluster ions in the decompression chamber, wherein the gas Cluster ions contain carbon atoms; accelerate the gas cluster ions in the decompression chamber to form an accelerated gas cluster ion beam along the beam path; promote at least a portion of the accelerated gas cluster ions along the beam path to fragment and// Or dissociation; removing charged particles from the beam path to form an accelerated neutral beam along the beam path in the decompression chamber; introducing a patterned template and the substrate into the decompression chamber; the base The material remains in the beam path; using the accelerated neutral beam, a portion of the surface of the substrate is irradiated through the opening of the patterned template to process it so that by implanting carbon atoms into the irradiated portion of the surface Forming a hardened and/or densified carbon-containing patterned layer on the irradiated part of the surface; separating the template and the substrate; etching the surface with the carbon-containing patterned layer for the first time to preferentially remove the surface One or more trenches and one or more plateau areas are formed from the material without carbon parts; a hard mask layer is formed on the plateau areas and trenches; Flatten the hard mask layer to remove it from the plateau area instead of the trench; and selectively use the hard mask layer as a mask for the second etching of the surface to remove the substrate material. 如請求項1之方法,其中該移除步驟基本上從該束路徑中移除全部帶電顆粒。 The method of claim 1, wherein the removing step substantially removes all charged particles from the beam path. 如請求項1之方法,進一步在該移除步驟後包括一熱處理該基材的步驟。 The method of claim 1, further comprising a step of heat treating the substrate after the removing step. 如請求項1之方法,其中該中性束基本上由來自該氣體簇離子束的氣體組成。 The method of claim 1, wherein the neutral beam consists essentially of gas from the gas cluster ion beam. 如請求項1之方法,其中該促進步驟包括在加速步驟中提高加速電壓,或改良在形成該氣體簇離子束時的離子化效率。 The method of claim 1, wherein the promoting step includes increasing the accelerating voltage in the accelerating step, or improving the ionization efficiency when forming the gas cluster ion beam. 如請求項1之方法,其中該促進步驟包括增加在該加速的氣體簇離子束中之離子速度範圍。 The method of claim 1, wherein the promoting step includes increasing the ion velocity range in the accelerated gas cluster ion beam. 如請求項1之方法,其中該促進步驟包括將一或多種使用來形成該氣體簇離子束的氣體元素引進該減壓艙中,以沿著該束路徑增加壓力。 The method of claim 1, wherein the promoting step includes introducing one or more gas elements used to form the gas cluster ion beam into the decompression chamber to increase the pressure along the beam path. 如請求項1之方法,其中該促進步驟包括以輻射能量照射該加速的氣體簇離子束或中性束。 The method of claim 1, wherein the promoting step includes irradiating the accelerated gas cluster ion beam or neutral beam with radiant energy. 如請求項1之方法,其中該處理工件表面之至少一部分的中性束實質上由具有能量在1電子伏特至數千電子伏特間之單體組成。 The method of claim 1, wherein the neutral beam that treats at least a portion of the workpiece surface consists essentially of a monomer having an energy between 1 electron volt and thousands of electron volts. 如請求項1之方法,該處理步驟進一步包括使用該加速 的中性束掃描該基材以處理該表面的延伸部分。 As in the method of claim 1, the processing step further includes using the acceleration The neutral beam scans the substrate to treat the extended portion of the surface. 如請求項1之方法,其中該基材包含結晶或非晶矽。 The method of claim 1, wherein the substrate comprises crystalline or amorphous silicon. 如請求項1之方法,其中該處理步驟形成一SiCx(0.05<X<3)層。 The method of claim 1, wherein the processing step forms a SiC x (0.05<X<3) layer. 如請求項1之方法,其中該硬遮罩層包含二氧化矽。 The method of claim 1, wherein the hard mask layer comprises silicon dioxide. 如請求項1之方法,其中該第一次蝕刻步驟使用包含氬之第二加速的中性束。 The method of claim 1, wherein the first etching step uses a second accelerated neutral beam containing argon. 如請求項1之方法,其中該第二次蝕刻步驟使用Cl2或CCl2F5電漿蝕刻技術。 The method of claim 1, wherein the second etching step uses Cl 2 or CCl 2 F 5 plasma etching technology. 如請求項1之方法,其中該加速步驟係透過5至50千伏的電壓加速該氣體簇離子。 The method of claim 1, wherein the acceleration step is to accelerate the gas cluster ions by a voltage of 5 to 50 kV. 如請求項1之方法,其中該處理步驟植入碳原子至每平方公分1x1014至5x1016個離子之預定劑量。 The method of claim 1, wherein the processing step implants carbon atoms to a predetermined dose of 1x10 14 to 5x10 16 ions per square centimeter. 如請求項1之方法,其中該含碳圖案化層具有約1至約3奈米之厚度。 The method of claim 1, wherein the carbon-containing patterned layer has a thickness of about 1 to about 3 nanometers. 如請求項1之方法,其中該第二次蝕刻步驟留下與該硬遮罩區域的底部共平面之該基材表面。 The method of claim 1, wherein the second etching step leaves the substrate surface coplanar with the bottom of the hard mask area. 一種在基材表面上的圖案化硬遮罩,其係藉由如請求項1之步驟形成。 A patterned hard mask on the surface of a substrate is formed by the steps as in claim 1.
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