TW201811543A - Fabrication of three-dimensional materials gradient structures by in-flight curing of aerosols - Google Patents

Abstract

A method for fabricating three-dimensional structures. In-flight heating, evaporation, or UV illumination modifies the properties of aerosol droplets as they are jetted onto a target surface. The UV light at least partially cures photopolymer droplets, or alternatively causes droplets of solvent-based nanoparticle dispersions to rapidly dry in-flight, and the resulting increased viscosity of the aerosol droplets facilitates the formation of free standing three-dimensional structures. This 3D fabrication can be performed using a wide variety of photopolymer, nanoparticle dispersion, and composite materials. The resulting 3D shapes can be free standing, fabricated without supports, and can attain arbitrary shapes by manipulating the print nozzle relative to the target substrate. Multiple materials may be mixed and deposited to form structures with compositionally graded material profiles, for example Bragg gratings in a light pipe or optical fiber, optical interconnects, and flat lenses.

Description

藉由噴霧的飛行中固化之三維材料梯度結構的製造技術Manufacturing technology of three-dimensional material gradient structure solidified by in-flight by spray

相關申請案之交叉引用 本申請案請求於2016年8月10日提申之美國臨時專利申請案第62/372,955,354號，標題“AEROSOL JET® 3D MATERIALS GRADIENTS”之優先權以及權益。本申請案亦為於2016年2月10日提申之美國專利申請案第15/040,878號，標題“FABRICATION OF THREE- DIMENSIONAL STRUCTURES BY IN-FLIGHT CURING OF AEROSOLS”之部分連續申請案，此申請案請求於2015年2月10日提申之美國臨時專利申請案第62/114,354號，標題“MICRO 3D PRINTING”之優先權以及權益。其等之說明書以及申請專利範圍在此併入本案以為參考。 發明領域CROSS-REFERENCE TO RELATED APPLICATIONS This application claims priority to and the benefit of the benefit of the benefit of the benefit of the benefit of the benefit of the benefit of the benefit of the benefit of the benefit of the benefit of the benefit of the benefit of the benefit of the benefit of the benefit of the benefit of the benefit of the benefit of the benefit of the benefit of the benefit of the benefit of the present disclosure. This application is also a continuation-in-part of the U.S. Patent Application Serial No. 15/040,878, entitled "FABRICATION OF THREE- DIMENSIONAL STRUCTURES BY IN-FLIGHT CURING OF AEROSOLS", filed on February 10, 2016. U.S. Provisional Patent Application Serial No. 62/114,354, entitled "MICRO 3D PRINTING", which is hereby incorporated by reference. The specification and the scope of the patent application are incorporated herein by reference. Field of invention

本發明有關藉由噴霧射出的奈米粒子以及聚合物墨水的飛行中固化之3D電氣與機械結構、微結構以及奈米結構之製造。The present invention relates to the manufacture of 3D electrical and mechanical structures, microstructures, and nanostructures of in-flight solidified nanoparticles by spray injection of nanoparticles and polymer inks.

發明背景 注意，下列討論會參考許多公開以及參考文獻。在此，此等公開文獻之討論，係為提供更完整的科學理論之背景知識，而不應被解釋成承認此公開文獻為在決定專利性質時之先前技術。BACKGROUND OF THE INVENTION Note that the following discussion refers to many publications and references. The discussion of such publications herein is intended to provide a more complete background of the scientific theory and should not be construed as an admission that this disclosure is prior art in determining the nature of the patent.

三維列印是一個快速發展的技術，其有可能使增量製造(additive manufacturing)徹底變革。利用3D列印，可在不需要切削機械加工或蝕刻步驟之情況下，將各種諸如塑膠以及金屬之結構材料，製成淨形結構。極少的材料浪費以及減少製程步驟，使3D列印可能成為符合成本效益之綠色技術。許多3D列印技術是目前可得的，簡單地比較此等技術與本發明會很有用。Three-dimensional printing is a rapidly evolving technology that has the potential to revolutionize additive manufacturing. With 3D printing, various structural materials such as plastic and metal can be made into a net shape without the need for cutting machining or etching steps. Minimal material waste and reduced process steps make 3D printing a cost-effective green technology. Many 3D printing techniques are currently available, and it would be useful to simply compare such techniques to the present invention.

立體微影技術是一種增量製造方法，其操作是藉由將紫外線(UV)雷射聚焦於光聚合物樹脂槽上。在電腦輔助製造或電腦輔助設計(CAM/CAD)軟體之幫助下，用UV雷射在光聚合物槽之表面上繪製一預編程設計或形狀。因為光聚合物在紫外線下是光敏性的，所以受到照射的樹脂會固化而形成所欲的3D物件中之單一層。針對設計的每一層重複此方法，直到3D物件完成。層解析度典型地50-150um，橫向尺寸接近10um。此方法一般而言限於光聚合物材料以及需要犧牲結構來支撐懸垂部分。Stereo lithography is an incremental manufacturing method that operates by focusing ultraviolet (UV) laser light onto a photopolymer resin bath. A pre-programmed design or shape is drawn on the surface of the photopolymer tank with UV lasers with the aid of computer aided manufacturing or computer aided design (CAM/CAD) software. Because the photopolymer is photosensitive under ultraviolet light, the irradiated resin will solidify to form a single layer in the desired 3D article. This method is repeated for each layer of the design until the 3D object is completed. The layer resolution is typically 50-150 um and the lateral dimension is close to 10 um. This method is generally limited to photopolymer materials and requires a sacrificial structure to support the overhang.

噴墨技術典型地用於以2D方式列印石墨以及顏料墨水。近來的材料發明，使得噴墨列印能夠噴射聚合以及金屬奈米粒子墨水。一般而言，噴墨列印中使用之墨水必須具有相對低的黏度，意思是墨水在列印後會大幅地擴散，因此限制了列印特徵之最小特徵尺寸以及縱橫比。墨水噴射器不接觸基材，但很靠近(小於mm)。Inkjet technology is typically used to print graphite and pigment inks in a 2D manner. Recent material inventions have enabled ink jet printing to be capable of jet polymerization as well as metallic nanoparticle inks. In general, the ink used in ink jet printing must have a relatively low viscosity, meaning that the ink will diffuse significantly after printing, thus limiting the minimum feature size and aspect ratio of the printing features. The ink ejector does not touch the substrate but is very close (less than mm).

擠出技術在熱塑性聚合物之3D列印方面很受歡迎。此情況下是將噴嘴中之熱性塑料加熱至熔點，然後擠至基材上。塑料在接觸的基材上快速地冷卻與固化並可維持三維形狀。3D部分典型地是一層一層製造的，各層包含擠出細絲之光柵圖案。懸垂部分可藉由擠出一犧牲支撐材料，之後溶解或以機械方式移除該支撐結構而製成。典型地特徵尺寸為數百微米，而材料很大程度被限制至熱塑性以及少數的熱固性聚合物以及導電膠。nScript工具能夠利用自動CAD/CAM控制定位噴嘴，在3D表面上列印。Extrusion technology is very popular in 3D printing of thermoplastic polymers. In this case, the hot plastic in the nozzle is heated to the melting point and then extruded onto the substrate. The plastic cools and solidifies rapidly on the contacting substrate and maintains a three-dimensional shape. The 3D portions are typically fabricated in layers, each layer comprising a grating pattern of extruded filaments. The overhanging portion can be made by extruding a sacrificial support material, then dissolving or mechanically removing the support structure. Typical feature sizes are hundreds of microns, while materials are largely limited to thermoplastics as well as a few thermoset polymers and conductive pastes. The nScript tool is capable of printing on a 3D surface using automatic CAD/CAM control positioning nozzles.

發明概要 本發明是一種用於在基材上製造三維結構之方法，該方法包含將噴霧液滴從一沉積頭推至該基材上，部分地改變在飛行中之噴霧液滴的特性，以及當該噴霧液滴沉積成為該三維結構之一部分時，完全改變其等之特性。改變特性任擇地包含使用電磁輻射之固化，例如，紫外線(UV)固化或硬化。在此具體例中，噴霧液滴較佳地包含光可固化聚合物，以及所製得的三維結構包含固化的聚合物。該噴霧液滴任擇地包含分散在光可固化聚合物中之固態粒子，而所製得的三維結構包含固化的聚合物，其包含包埋的固態粒子。該固態粒子任擇地包括陶瓷、金屬、纖維或矽。在另一具體例中，該噴霧液滴包含溶劑，而改變特性包含蒸發該溶劑。此等噴霧液滴任擇地包含金屬奈米粒子，在此情況下，該方法較佳地另外包含用UV輻射照射該噴霧液滴、加熱該金屬奈米粒子以及充分地加熱該噴霧液滴至至少部分地蒸發該溶劑。該方法較佳地另外包含在其等已經沉積之後，持續照射該金屬奈米粒子，從而至少部份地燒結該金屬奈米粒子。SUMMARY OF THE INVENTION The present invention is a method for making a three-dimensional structure on a substrate, the method comprising pushing a spray droplet from a deposition head onto the substrate, partially altering the characteristics of the spray droplets in flight, and When the spray droplets are deposited as part of the three-dimensional structure, their properties are completely changed. The changing characteristics optionally include curing using electromagnetic radiation, such as ultraviolet (UV) curing or hardening. In this embodiment, the spray droplets preferably comprise a photocurable polymer, and the resulting three dimensional structure comprises a cured polymer. The spray droplets optionally comprise solid particles dispersed in a photocurable polymer, and the resulting three-dimensional structure comprises a cured polymer comprising embedded solid particles. The solid particles optionally comprise ceramic, metal, fiber or ruthenium. In another embodiment, the spray droplets comprise a solvent, and changing the property comprises evaporating the solvent. The spray droplets optionally comprise metal nanoparticles, in which case the method preferably additionally comprises irradiating the spray droplets with UV radiation, heating the metal nanoparticles, and substantially heating the spray droplets to The solvent is at least partially evaporated. The method preferably further comprises, after it has been deposited, continuously illuminating the metal nanoparticles to at least partially sinter the metal nanoparticles.

該方法任擇地包含相對於該基材傾斜或移動該沉積頭。該方法任擇地包含在不需要犧牲支撐物或傾斜該沉積頭或該基材之情況下，製造懸垂結構。該沉積頭與該基材間之噴射距離(standoff distance)，較佳地至少1mm，更佳地至少2mm。該方法較佳地包含增加該噴霧液滴在飛行中之黏度，以及較佳地包含用電磁輻射照射在飛行中以及在該噴霧液滴已經沉積後之噴霧液滴，任擇地在飛行中，從超過一個方向照射。該方法任擇地包含用電磁輻射加熱在飛行中以及在該噴霧液滴已經沉積後之噴霧液滴。製得的三維結構任擇地包含選自於由下列所構成之群組之結構：微米量級之表面紋理、機械中介層(mechanical interposer)、精密墊片、包含包埋電連接器之機械中介層、封閉中空結構、機械支架以及功能性電線。The method optionally includes tilting or moving the deposition head relative to the substrate. The method optionally includes fabricating the overhang structure without sacrificing the support or tilting the deposition head or the substrate. The standoff distance between the deposition head and the substrate is preferably at least 1 mm, more preferably at least 2 mm. The method preferably includes increasing the viscosity of the spray droplets during flight, and preferably comprising spraying the droplets in flight with electromagnetic radiation and after the spray droplets have been deposited, optionally in flight, Illuminate from more than one direction. The method optionally includes heating the spray droplets in flight with electromagnetic radiation and after the spray droplets have been deposited. The resulting three-dimensional structure optionally comprises a structure selected from the group consisting of micron-sized surface textures, mechanical interposers, precision shim, and mechanical intermediaries including embedded electrical connectors. Layers, closed hollow structures, mechanical supports, and functional wires.

本發明之目的、優點以及新穎特徵，以及適用性之進一步範疇，有些將在下面詳細的說明中，結合所附之圖式作說明，而有些對在檢視下列或從本發明實例中學習後之熟悉此技藝之人士而言，將變得顯而易見。憑藉附加的申請專利範圍中指出之手段以及組合，可理解以及獲得本發明之目的以及優點。The objects, advantages and novel features of the invention, as well as further scope of applicability, will be described in the following detailed description in conjunction with the accompanying drawings. It will become apparent to those skilled in the art. The objects and advantages of the invention will be understood and attained by the <RTIgt;

較佳實施例之詳細說明 本發明是一種使用噴霧以及墨水的飛行中固化來製造三維結構，諸如包含高縱橫比特徵之結構之方法，以及直接列印液態材料以製造三維、自立的複合結構之方法。明確而言，本發明之具體例結合了諸如在美國專利案第7,674,671號、第7,938,079號以及第7,987,813號中所述之獲得專利的噴霧噴射分配技術以及飛行中之材料加工機制，其使得液態液滴在沉積於表面上之前部分地硬化。在飛行中加工之後，液滴可沉積下來形成自立的結構。此方法之一些優點包括超高解析度三維(3D)列印，特徵尺寸降至10微米，橫向特徵解析度至1微米以及垂直解析度至100nm。該自立結構之縱橫比可超過100，且可藉由操縱列印頭相對於該等表面之傾斜度以及位置，在幾乎任何表面以及表面幾何形狀上列印該結構。懸垂以及閉孔可直接列印，不須使用犧牲支撐材料。金屬與絕緣材料均可加工，其使得能夠共沉積用於製造3D電路之電子材料。此外，可列印複合材料，此容許定制具機械與電氣特性之3D結構。紫外線(UV)聚合物可在其等正撞擊至標的之飛行中固化，以及低燒結溫度使能夠在塑料表面金屬化。使用噴霧噴射方法，實際上任何類型之材料和/或溶劑均可列印。此方法中，與基材間大的噴射距離(典型地幾毫米)，使能夠在無任何z-軸移動之情況下進行高縱橫比列印。亞10微米的噴霧噴射聚焦，使能夠製造超細特徵。DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention is a method of fabricating a three-dimensional structure, such as a structure comprising high aspect ratio features, using a spray and ink in-vivo, and directly printing a liquid material to produce a three-dimensional, self-standing composite structure. method. In particular, the specific examples of the present invention incorporate a patented spray-jet dispensing technique as described in U.S. Patent Nos. 7,674,671, 7,938, 079, and 7, 987, 813, and in-flight material processing mechanisms which enable liquid liquids The drops partially harden before being deposited on the surface. After processing in flight, the droplets can be deposited to form a self-standing structure. Some of the advantages of this approach include ultra-high resolution three-dimensional (3D) printing with feature sizes down to 10 microns, lateral feature resolution to 1 micron, and vertical resolution to 100 nm. The free-standing structure can have an aspect ratio in excess of 100 and can be printed on almost any surface and surface geometry by manipulating the inclination and position of the print head relative to the surfaces. Overhangs and closed cells can be printed directly without the use of sacrificial support materials. Both metal and insulating materials can be processed which enable co-deposition of electronic materials used to fabricate 3D circuits. In addition, composite materials can be printed, which allows customization of 3D structures with mechanical and electrical properties. Ultraviolet (UV) polymers can be cured in flight in which they are hitting the target, and low sintering temperatures enable metallization on the plastic surface. With the spray jet method, virtually any type of material and/or solvent can be printed. In this method, a large jet distance (typically a few millimeters) from the substrate enables high aspect ratio printing without any z-axis movement. Sub-10 micron spray jet focusing enables the fabrication of ultra-fine features.

噴霧噴射列印是一種非接觸式、噴霧基的噴射技術。起始墨水是配製成低黏度(0.5至1000cP)，且在典型的方法中，其等先被霧化成1-5mm直徑液滴之細液滴分散物。較佳地氮氣帶著液滴以及透過細噴嘴(0.1-1mm內徑)將其等推至供沉積之標的基材。併流，較佳地氮鞘氣，會將液滴噴射聚焦縮小至10mm直徑，其容許列印具此大小之特徵。噴射技術值得注意的是噴嘴以及基材間之大噴射距離(數mm)、細解析度(特徵寬10mm)、體積分配精準度(10毫微微升)以及廣泛的材料相容性。因為噴射距離大，所以在液滴飛行至基材期間，乾燥和/或以其它方式固化液滴係可能的。在這情況下，液滴之黏度可能增加遠遠的超過起始黏度。在較高的黏度下，列印的墨水可自我支撐，且可堆積成自立管柱以及其它高縱橫比特徵。為了增加黏度，較佳地在噴嘴出口與標的基材間之間隙區域，施用從燈管或UV LED而來之UV光，如圖1A-1C所示。假如起始墨水包含具吸收帶與UV發出光譜重疊之光聚合物，則該UV光可完全或部分地固化在飛行中之光聚合物液滴，從而增加黏度。Spray jet printing is a non-contact, spray-based jetting technique. The starting ink is formulated to a low viscosity (0.5 to 1000 cP), and in a typical process, it is first atomized into a fine droplet dispersion of 1-5 mm diameter droplets. Preferably, the nitrogen is carried with droplets and through a fine nozzle (0.1-1 mm inner diameter) to push it onto the substrate for deposition. Cocurrent flow, preferably nitrogen sheath gas, will reduce the droplet ejection focus to a diameter of 10 mm, which allows for the printing of features of this size. Jet technology is notable for large jet distances (mm) between nozzles and substrates, fine resolution (features of 10 mm), volumetric accuracy (10 femtoliters), and extensive material compatibility. Because of the large spray distance, it is possible to dry and/or otherwise cure the droplets during flight of the droplets to the substrate. In this case, the viscosity of the droplets may increase far beyond the initial viscosity. At higher viscosities, the printed ink is self-supporting and can be stacked into self-standing columns and other high aspect ratio features. In order to increase the viscosity, it is preferred to apply UV light from the tube or UV LED in the interstitial region between the nozzle outlet and the target substrate, as shown in Figures 1A-1C. If the starting ink comprises a photopolymer having an absorption band that overlaps the UV emission spectrum, the UV light can completely or partially cure the photopolymer droplets in flight, thereby increasing the viscosity.

圖11顯示本發明之裝置之一具體例。載送氣體10 以箭頭所指之方向流進第一霧化器30 且使材料26 霧化形成噴霧材料31 ，如奈米粒子墨水。載送氣體11 以箭頭所指之方法流進第二霧化器32 且使第二材料27 霧化形成噴霧材料33 。黏度1-10cP之材料最好是用超音波氣霧器來霧化。黏度10-1,000cP之材料最好是用氣動氣霧器來霧化。黏度大於1,000 cP之材料可用適合的稀釋劑修改至適合氣動霧化之黏度。噴霧材料31 、33 可被該載送氣體推動而以箭頭所指之方向流經(例如)管道至混合槽34 ，其等在此結合。該噴霧混合物之後會流進沈積頭22 。鞘氣12 以箭頭所指之方向流進沈積頭22 以及圍繞著該結合的噴霧流製造出一聚焦液滴噴射流36 。該液滴噴射流36 離開沈積噴嘴24 ，以及在該材料包含光聚合物之具體例中，使用光37 ，例如UV光固化該液滴，其以擺動箭頭所指之方向照射，之後撞擊標的28 。沈積噴嘴24 與標的28 間之距離可為任何從1mm至高如10mm之距離，但較佳地介在大約2mm與5mm之間。改變相對載氣之流動，會改變兩種材料的相對沉積速率。在一或多個具體例中，該二種材料可包含不同折射率n1、n2。Figure 11 shows a specific example of the apparatus of the present invention. The carrier gas 10 flows into the first atomizer 30 in the direction indicated by the arrow and atomizes the material 26 to form a spray material 31 , such as nanoparticle ink. The carrier gas 11 flows into the second atomizer 32 in the manner indicated by the arrow and atomizes the second material 27 to form the spray material 33 . The material with a viscosity of 1-10 cP is preferably atomized by an ultrasonic aerosolizer. The material having a viscosity of 10-1,000 cP is preferably atomized by a pneumatic aerosolizer. Materials with a viscosity greater than 1,000 cP can be modified to a viscosity suitable for pneumatic atomization with a suitable diluent. The spray material 31 , 33 can be pushed by the carrier gas and flow through, for example, a conduit to the mixing tank 34 in the direction indicated by the arrow, where it is combined. The spray mixture then flows into the deposition head 22 . The sheath gas 12 flows into the deposition head 22 in the direction indicated by the arrow and a focused droplet jet 36 is produced around the combined spray stream. The droplet jet stream 36 exits the deposition nozzle 24 , and in the particular example where the material comprises a photopolymer, the droplet is cured using light 37 , such as UV light, which is illuminated in the direction indicated by the oscillating arrow, and then strikes the target 28 . The distance between the deposition nozzle 24 and the target 28 can be any distance from 1 mm up to 10 mm, but preferably between about 2 mm and 5 mm. Changing the flow of the relative carrier gas changes the relative deposition rate of the two materials. In one or more specific examples, the two materials can comprise different refractive indices n1, n2.

圖1A是描述噴霧噴射3D列印之機制之示意圖。微3D結構最好是使用噴霧噴射相容的低黏度光可固化樹脂或光聚合物，較佳地使用以上所述之噴霧噴射技術列印來製造。電磁輻射，在此例子中是紫外線，照射以及部分地固化飛行中之液滴。該部分固化會增加光聚合物液滴的黏度，其反過來限制基材上之沉積物的擴散。該光聚合物液滴較佳地在該標的基材上合成一體，然後完全固化。圖1B顯示包含材料31 、33 二者之光聚合物液滴垂直堆疊形成沈積物50 。三維沈積物50 包含組份分級材料剖面，較佳地藉由改變將共沈積之不同材料的相對氣流或粉料進料速率達成。該材料較佳地包含粒子與UV活化聚合物之混合物。固化在沈積噴嘴24 與標的28 之間飛行之液滴，可在不需要燒結或加熱該標的之情況下幫助快速地硬化到位的材料31 、33 ，其使得可列印自立梯度3D沈積物50 。光37 較佳地從該液滴流以及沈積物之二側照射進行固化。光37 之波長最好是與該材料中所含之聚合物中之活化劑如UV活化劑匹配。圖1C顯示光聚合物液滴在標的28 於該沈積頭下方平移時形成懸垂結構51 。選擇性地，可移動該沈積頭，而該標的保持不動。示範高達45度之懸垂結構，然而可達到甚至更大的角度。Figure 1A is a schematic diagram depicting the mechanism of spray jet 3D printing. The micro 3D structure is preferably manufactured using a spray-spray compatible low viscosity photocurable resin or photopolymer, preferably printed using the spray jet technique described above. Electromagnetic radiation, in this case ultraviolet light, illuminates and partially solidifies droplets in flight. This partial cure increases the viscosity of the photopolymer droplets, which in turn limits the diffusion of deposits on the substrate. The photopolymer droplets are preferably integrated on the target substrate and then fully cured. Figure IB shows the photopolymer droplets comprising both materials 31 , 33 stacked vertically to form a deposit 50 . The three-dimensional deposit 50 comprises a component grading material profile, preferably by varying the relative gas flow or powder feed rate of the different materials to be co-deposited. The material preferably comprises a mixture of particles and a UV activated polymer. Curing the droplets flying between the deposition nozzle 24 and the target 28 helps to quickly harden the in place material 31 , 33 without the need to sinter or heat the target, which allows the self-standing gradient 3D deposit 50 to be printed. Light 37 is preferably cured by irradiation from both the stream of droplets and the side of the deposit. Preferably, the wavelength of light 37 is matched to an activator such as a UV activator in the polymer contained in the material. Figure 1C shows that the photopolymer droplets form a pendant structure 51 as the target 28 translates beneath the deposition head. Optionally, the deposition head can be moved while the target remains stationary. Demonstrate a suspended structure of up to 45 degrees, however an even larger angle can be achieved.

圖2A是用Loctite 3104丙烯酸胺基甲酸乙酯以及同時UV LED固化列印之直立聚合物柱之照片。入射UV功率為0.65mW，UV波長為385nm以及容積列印速率為7.5nL/s。該等柱可從該標的基材實質上延伸至該噴霧噴射噴嘴之出口。圖2B是該柱陣列之放大影像；該柱之高度為1.0mm，高度變異為1%，間隔為0.5mm以及直徑為90mm。圖2C是該柱陣列之頂表面之影像。各柱之頂部形狀是圓的，近半球形。圖2D是顯示所測得之單柱建造速率之圖。發現，當列印噴嘴固定在一指定位置時(即，停留時間)，柱高度與時間成正比。高度之變異大約為1%，或選擇性地對1.0mm高之柱而言，大約10mm。Figure 2A is a photograph of an upright polymer column printed with Loctite 3104 urethane acrylate and simultaneous UV LED curing. The incident UV power was 0.65 mW, the UV wavelength was 385 nm, and the volume printing rate was 7.5 nL/s. The columns can extend substantially from the target substrate to the exit of the spray jet nozzle. Figure 2B is an enlarged image of the column array; the column has a height of 1.0 mm, a height variation of 1%, a spacing of 0.5 mm, and a diameter of 90 mm. Figure 2C is an image of the top surface of the column array. The top shape of each column is round and nearly hemispherical. Figure 2D is a graph showing the measured single column build rate. It was found that when the print nozzle was fixed at a specified position (i.e., residence time), the height of the column was proportional to time. The height variation is about 1%, or alternatively about 1.0 mm for a 1.0 mm tall column.

當固態粒子，諸如陶瓷、金屬或纖維，分散於光聚合物墨水中時，飛行中之加工方法亦是可能的。在此情況下中，固化的光聚合物作為固態粒子之3D機械支撐物。此複合材料之機械與電氣特性，可經由如提供耐磨性以及形成3D電導體而得到最佳化。圖3是複合柱陣列之影像。將具粒徑小於500nm之矽粉，以7重量%之濃度分散於UV光聚合物樹脂中。之後將該複合分散物列印以及在飛行中固化，產生包埋矽之固化樹脂的實心柱。柱直徑為120mm，高度為1.1mm。複合材料對最佳化3D結構之機械以及電氣特性是有利的。在此例子中，該複合材料對UV光而言夠透明，所以即使單邊照射UV，亦可完全固化。在更高的濃度以及具有高度吸收性粒子之情況下，複合樹脂可能無法使入射光透過。在此情況下，需要從反側照射列印區域，或用環燈照射沉積物。只要在3D結構之外表面附近的UV樹脂固化，則有足夠的機械支撐力容許結構在垂直方向上建造。在柱加工步驟中，可任擇地藉由，例如加熱該3D結構至超過該光聚合物之蒸發或分解點而移除光聚合物。In-flight processing methods are also possible when solid particles, such as ceramics, metals or fibers, are dispersed in the photopolymer ink. In this case, the cured photopolymer acts as a 3D mechanical support for the solid particles. The mechanical and electrical properties of the composite can be optimized by, for example, providing wear resistance and forming a 3D electrical conductor. Figure 3 is an image of a composite column array. Tantalum powder having a particle diameter of less than 500 nm was dispersed in a UV photopolymer resin at a concentration of 7% by weight. The composite dispersion is then printed and cured in flight to produce a solid column encapsulating the cured resin of the crucible. The column has a diameter of 120 mm and a height of 1.1 mm. Composite materials are advantageous for optimizing the mechanical and electrical properties of the 3D structure. In this example, the composite is sufficiently transparent to UV light, so that it can be fully cured even if UV is unilaterally illuminated. At higher concentrations and with highly absorbing particles, the composite resin may not be able to transmit incident light. In this case, it is necessary to illuminate the printing area from the opposite side or to illuminate the deposit with a ring light. As long as the UV resin near the surface of the 3D structure is cured, there is sufficient mechanical support to allow the structure to be built in the vertical direction. In the column processing step, the photopolymer can optionally be removed by, for example, heating the 3D structure beyond the point of evaporation or decomposition of the photopolymer.

圖4顯示列印的機械中介層之影像，其是可提供二個分開的組件間之結構支撐以及精密間隔之元件。該中介層是經由堆疊數層UV樹脂列印而成，可見圖4A之透視圖。圖4B顯示頂表面網格圖案。在一些具體例中，中介層可在元件之間或連接至另一個之間，提供電氣或流體通路，在此情況下，該間隙間隔可充填導電材料或流體。Figure 4 shows an image of a printed mechanical interposer that provides structural support between two separate components and precisely spaced components. The interposer is printed by stacking several layers of UV resin, as seen in the perspective view of Figure 4A. Figure 4B shows a top surface mesh pattern. In some embodiments, the interposer can provide an electrical or fluid path between the elements or between the other, in which case the gap spacing can be filled with a conductive material or fluid.

圖5A顯示使用圖1所示之偏移方法列印之三維似鐵叉(jack-like)結構。下面4個腳是列印頭在x以及y方向上移動至頂點列印而成。柱相對於基材大約傾斜45度。頂腳是列印頭移動離開頂點列印而成。總高度是4mm，個別柱直徑為60mm。圖5B顯示開放圓錐體結構。此係利用將平台以漸增半徑重複環狀移動列印而得。需要時，可藉由連續環狀移動以及將半徑減少至0而封閉此圓錐體。Figure 5A shows a three-dimensional jack-like structure printed using the offset method shown in Figure 1. The following four feet are printed by the print head moving to the apex in the x and y directions. The column is tilted approximately 45 degrees relative to the substrate. The top foot is printed by the print head moving away from the apex. The total height is 4mm and the individual columns are 60mm in diameter. Figure 5B shows the open cone structure. This is achieved by repeating the circular movement of the platform with increasing radius. If desired, the cone can be closed by continuous annular movement and reducing the radius to zero.

圖6A以及6B顯示具有沿著長度之開放內部之密閉管道。該管道之各側壁，是藉由堆疊光可固化聚合物之線以及連續地偏移大約線寬的½列印而得。此方法在偏移方向上產生一傾斜大約45度之壁。以相反方向偏移，壁會在中間點接觸。圖6C描述一滴放置在管道入口附近之染色墨水，其似乎因表面張力而被拉通過管道。此證明，管道沿著長度是封閉的，但端至端是完全開放的。Figures 6A and 6B show a closed conduit having an open interior along the length. The side walls of the tube are obtained by stacking lines of photocurable polymer and continuously offset by about 1⁄2 of the line width. This method produces a wall that is inclined at approximately 45 degrees in the direction of the offset. Offset in the opposite direction, the wall will contact at the intermediate point. Figure 6C depicts a drop of dyed ink placed near the entrance to the pipe that appears to be drawn through the pipe due to surface tension. This proves that the pipe is closed along the length, but the end is completely open.

圖7A顯示一種作為電氣組件之機械支撐物之光固化柱。聚合物柱是使用圖1中之方法製得，其大約1mm高，0.1mm寬。藉由使列印頭對每一個傾斜45度，將銀墨水列印在柱以及基材之側壁上。在列印期間，銀墨水具低黏度，因此在基材上會慢慢擴散。因提供了機械支撐，故可沿著支撐物之表面三維列印銀墨水。列印後，在烤箱中以150°C熱燒結該銀墨水60分鐘。所產生的導電圖案用作為自立、毫米波偶極天線。圖7B顯示微天線之陣列。圖7C以及7D是列印在微晶片上之3D電氣組件之影像。本發明之方法排除需以其它方式建構成一組件之複雜的連結以及導波管。此例子顯示諸如3D電氣組件之功能性元件(例如，加熱器、天線以及連接線)，可直接列印在驅動晶片上。Figure 7A shows a photocuring column as a mechanical support for an electrical component. The polymer column was made using the method of Figure 1, which was about 1 mm high and 0.1 mm wide. Silver ink is printed on the columns and the sidewalls of the substrate by tilting the print heads 45 degrees each. During printing, the silver ink has a low viscosity and therefore slowly spreads over the substrate. Due to the mechanical support, silver ink can be printed in three dimensions along the surface of the support. After printing, the silver ink was thermally sintered at 150 ° C for 60 minutes in an oven. The resulting conductive pattern is used as a self-standing, millimeter wave dipole antenna. Figure 7B shows an array of micro-antennas. Figures 7C and 7D are images of 3D electrical components printed on a microchip. The method of the present invention eliminates the need for complex connections and waveguides that are otherwise constructed to form a component. This example shows functional components such as 3D electrical components (eg, heaters, antennas, and connectors) that can be printed directly onto the driver wafer.

圖8A顯示利用列印期間傾斜列印頭製造之自立聚合物彈簧。在建構各個彈簧期間，列印頭從0°傾斜至-30°，然後回到0°。圖8B描述一個顯示該彈簧陣列可支撐一機械塊體之示範。與之前所述之立柱相反，彈簧在二個表面之間提供可撓性中介層連接。Figure 8A shows a self-standing polymer spring fabricated using a tilt print head during printing. During the construction of each spring, the print head is tilted from 0° to -30° and then back to 0°. Figure 8B depicts an illustration showing that the array of springs can support a mechanical block. In contrast to the previously described uprights, the spring provides a flexible interposer connection between the two surfaces.

在諸如金屬奈米粒子分散物之溶劑基墨水之例子方面，液滴黏度可藉由飛行期間部分或完全乾燥而增加。因為已知金屬奈米粒子會高度吸收UV光，所以將液滴曝露於UV照射可加熱奈米粒子以及加速溶劑蒸發。圖9顯示此一原位固化方法延伸至非光可固化材料。圖9A是顯示在UV波長下銀奈米粒子之光學密度(即，吸收光譜)，隨著粒徑減少而增加之圖。曲線在410nm附近有一強大的峰值，但吸收邊緣延伸至可見光，使得用一般的UV LED以及水銀燈來進行飛行中之方法成為可能。因此包含銀奈米粒子分散於溶劑中之墨水液滴，可因吸收近400nm波長之UV光而被加熱。若在飛行中加熱，則溶劑會大量地蒸發，因而當撞擊在表面上時，產生高度濃縮的銀滴。因為攜帶溶劑被蒸發了，亦因為粒子部分被燒結了，所以金屬奈米粒子液滴可保留其等之3D形狀。與光聚合物之堆疊之方式相似，現在較高黏度之銀液滴可以3D堆疊。列印後進一步的照射，會將奈米粒子加熱超過將溶劑蒸發所需之程度，使奈米粒子部分地燒結而變成導體。圖9B顯示用原位照射方法列印之3D銀線陣列。線寬為40mm，高為0.8mm。該等線稍微的彎曲，因為事實上僅使用單側照射，此使照射側上之線得到較多的加熱，導致不對稱收縮。In the case of solvent based inks such as metal nanoparticle dispersions, the droplet viscosity can be increased by partial or complete drying during flight. Since metal nanoparticles are known to highly absorb UV light, exposure of the droplets to UV irradiation heats the nanoparticles and accelerates solvent evaporation. Figure 9 shows that this in-situ curing process extends to a non-photocurable material. Figure 9A is a graph showing the increase in optical density (i.e., absorption spectrum) of silver nanoparticles at UV wavelength as the particle size decreases. The curve has a strong peak near 410 nm, but the absorption edge extends to visible light, making it possible to fly in general with UV LEDs and mercury lamps. Therefore, ink droplets containing silver nanoparticles dispersed in a solvent can be heated by absorbing UV light having a wavelength of approximately 400 nm. If heated in flight, the solvent will evaporate in large amounts, thus producing highly concentrated silver droplets when struck on the surface. Since the carrier solvent is evaporated, and since the particle portion is sintered, the metal nanoparticle droplets can retain their 3D shape. Similar to the way light polymers are stacked, now higher viscosity silver droplets can be stacked in 3D. Further irradiation after printing will heat the nanoparticles more than necessary to evaporate the solvent, and the nanoparticles will be partially sintered to become a conductor. Figure 9B shows a 3D silver line array printed by in situ illumination. The line width is 40mm and the height is 0.8mm. The lines are slightly curved because virtually only one side illumination is used, which results in more heating of the lines on the illumination side, resulting in asymmetric shrinkage.

圖10A-10F是使用UV聚合物以及飛行中固化列印之各種3D形狀之影像。圖10A顯示柱狀體(0.1mm間距，0.25mm高)。圖10B顯示扭曲薄片(0.5mm寬，2mm高)。圖10C顯示盒狀體(1mm長，0.25mm高，0.03mm壁)。圖10D顯示帽狀體(0.5mm直徑，0.5mm高)。圖10E顯示錐狀體(0.5mm直徑，0.5mm高)。圖10F顯示泡狀體(0.5mm直徑，1mm高)。Figures 10A-10F are images of various 3D shapes using UV polymers and in-flight cured printing. Figure 10A shows a columnar body (0.1 mm pitch, 0.25 mm height). Figure 10B shows a twisted sheet (0.5 mm wide, 2 mm high). Figure 10C shows the box-like body (1 mm long, 0.25 mm high, 0.03 mm wall). Figure 10D shows the cap (0.5 mm diameter, 0.5 mm height). Figure 10E shows a cone (0.5 mm diameter, 0.5 mm height). Figure 10F shows a blister (0.5 mm diameter, 1 mm height).

在本發明之具體例中，UV照射是用於改變噴霧液滴在其等被噴射至標的表面時之特性。在一些具體例中，UV光至少部分地固化光聚合物液滴，以及所導致之黏度的增加，促進自立結構之形成。在其它具體例中，UV光使溶劑基奈米粒子分散物之液滴於飛行中快速地乾燥，同樣地使能夠3D製造。因此，根據本發明之3D製造可使用各式各樣的光聚合物、奈米粒子分散物以及複合材料進行。所產生的3D形狀可為自立的、不需要支撐，且可藉由相對於標的基材操縱列印噴嘴，獲得任意形狀。特徵尺寸主要由噴射方法決定，可縮小至10µm或甚至更小。In a specific embodiment of the invention, UV illumination is used to alter the characteristics of the spray droplets as they are ejected onto the surface of the target. In some embodiments, the UV light at least partially cures the photopolymer droplets, and the resulting increase in viscosity promotes the formation of a free standing structure. In other specific examples, the UV light causes the droplets of the solvent-based nanoparticle dispersion to rapidly dry in flight, and similarly enables 3D fabrication. Thus, 3D fabrication in accordance with the present invention can be carried out using a wide variety of photopolymers, nanoparticle dispersions, and composites. The resulting 3D shape can be self-standing, does not require support, and can be obtained in any shape by manipulating the print nozzle relative to the target substrate. The feature size is mainly determined by the ejection method and can be reduced to 10 μm or even smaller.

在圖12 所示之本發明之具體例中，與圖2A的相似之丙烯酸柱90 被列印在針頭92 上。此證明本發明之技術可在任何地方列印3D物件，包括列印在任何其它的3D表面上。針頭92 上之各種角度之丙烯酸柱90 證明，列印頭可對準任何表面，以任何角度列印至該表面。在其它競爭技術中，常需要從平面或乾淨表面開始列印。本發明可用於在既存的表面或部件上建立3D結構。此外，可使用相同的工具，於3D列印物件上列印電子元件，結合結構3D列印物件與3D電子元件。In the specific example of the invention shown in Fig. 12 , an acrylic column 90 similar to that of Fig. 2A is printed on the needle 92 . This demonstrates that the techniques of the present invention can print 3D objects anywhere, including printing on any other 3D surface. The acrylic column 90 at various angles on the needle 92 demonstrates that the print head can be aligned to any surface and printed to the surface at any angle. In other competing technologies, it is often desirable to print from a flat or clean surface. The invention can be used to create 3D structures on existing surfaces or components. In addition, the same tool can be used to print electronic components on the 3D printed object, in combination with the structure 3D to print the object and the 3D electronic component.

圖13A 、13B 以及13C 顯示形成在安裝發光二極體(LED)之表面上之丙烯酸柱100 。在本發明之此具體例中，該半透明丙烯酸柱作為一光管，用於引導光從一處至另一處，與光纖相似。光管是同一材料之圓柱，基本上為半透明管，其可連接二個光學元件 ，且其主要目的是在二個元件之間傳輸光。本發明之光管可為直的、彎曲的或斜角的之任意組合。此列印光管有可能省略光纖上之手動連接以及終結。光管可以應用於電子晶片間之高速光學互連、高帶寬通信、應變傳感器、光纖激光器和光學濾波器。 13A , 13B, and 13C show the acrylic column 100 formed on the surface on which the light emitting diode (LED) is mounted. In this embodiment of the invention, the translucent acrylic column acts as a light pipe for directing light from one location to another, similar to an optical fiber. The light pipe is a cylinder of the same material, basically a translucent tube that can connect two optical elements, and its main purpose is to transfer light between the two elements. The light pipe of the present invention can be any combination of straight, curved or beveled. This print light tube may omit manual connection and termination on the fiber. Light tubes can be used for high speed optical interconnects between electronic wafers, high bandwidth communications, strain sensors, fiber lasers, and optical filters.

在本發明之一具體例中，光管或光纖可包含聚合物折射率之調制，以便製造濾光器。此等調制可在折射率改變的地方反射光，且較佳地可用於製造布拉格濾光器。依照本發明製得之列印纖維之直徑可小如10µm，有或無材料梯度。圖14 描述此一具布拉格濾光器之光纖之具體例。入射光60 進入光纖核心62 (即，光管)且行經濾光器64 、66 、68 、70 、72 、74 、76 。濾濾光器64 、66 、68 、70 、72 、74 、76 較佳地具有不同的光學指數，因此會反射出不同波長的光80 ，產生所需的相長和/或相消干涉。在需要高光學反射率之情況下，可用金屬、反射性材料取代透明光學材料之一種。選擇性地，在需要於纖維中產生光之情況下，可用螢光材料取代該透明光學材料中之一種或添加於其中。In one embodiment of the invention, the light pipe or fiber may comprise a modulation of the refractive index of the polymer to produce a filter. Such modulation can reflect light where the index of refraction changes, and is preferably useful for fabricating Bragg filters. The diameter of the printed fibers produced in accordance with the present invention can be as small as 10 [mu]m with or without a material gradient. Fig. 14 shows a specific example of the optical fiber of this Bragg filter. Incident light 60 enters fiber core 62 (i.e., light pipe) and passes through filters 64 , 66 , 68 , 70 , 72 , 74 , 76 . The filter filters 64 , 66 , 68 , 70 , 72 , 74 , 76 preferably have different optical indices and therefore reflect light 80 of different wavelengths, producing the desired constructive and/or destructive interference. In the case where high optical reflectivity is required, one of the transparent optical materials may be replaced by a metal or a reflective material. Alternatively, in the case where light is required to be generated in the fiber, one of the transparent optical materials may be replaced with or added to the fluorescent material.

沿著纖維長度之材料梯度，較佳地包含空間方差或濾光器間之間隔下限為10nm。對於一些光學布拉格濾光器64 、66 、68 、70 、72 、74 、76 ，最佳的空間方差較佳地為250nm，大約可見光之波長的一半。假如用不同的噴霧氣體流混合該等材料，則沿著該纖維之長度之材料梯度可正弦變化。選擇性地，假如用脈衝流混合該等材料，則可在不連續的步驟中發生該材料梯度。該材料梯度振幅可從0變化至100%，取決於從各個霧化器進料之材料的相對數量。The material gradient along the length of the fiber preferably comprises a spatial variance or a lower spacing between the filters of 10 nm. For some optical Bragg filters 64 , 66 , 68 , 70 , 72 , 74 , 76 , the optimal spatial variance is preferably 250 nm, which is about half the wavelength of visible light. If the materials are mixed with different spray gas streams, the material gradient along the length of the fibers can be sinusoidally varied. Alternatively, if the materials are mixed with a pulsed stream, the material gradient can occur in discrete steps. The material gradient amplitude can vary from 0 to 100%, depending on the relative amount of material fed from each atomizer.

可在該光纖維之外面任擇的施用光學護套78 ，以改善該光纖內部核心62 之光封入。該光學護套較佳地具有比二個(或多個)用於該核心之材料低的折射率。例如，以螺旋形列印光學護套78 ，製造出一中空管柱，接著沿著該纖維軸列印具一或多種材料梯度之核心62 。該纖維側壁以及光學護套78 之粗糙度較佳地低於1微米，透過內部全反射，促進該核心內之光封入。光學材料較佳地包含透明光聚合物，其具有用於控制光反射所需之不同的折射率，但具類似的化學物質；例如，其等較佳地是可混溶的和/和具有相似的UV固化特性。An optical sheath 78 can be applied optionally on the outside of the optical fiber to improve light encapsulation of the inner core 62 of the fiber. The optical sheath preferably has a lower index of refraction than two (or more) materials for the core. For example, the optical sheath 78 is printed in a spiral shape to produce a hollow tubular string, followed by a core 62 of one or more material gradients printed along the fiber axis. The fiber sidewalls and the optical sheath 78 preferably have a roughness of less than 1 micrometer and are internally totally reflective to promote light encapsulation within the core. The optical material preferably comprises a transparent photopolymer having a different refractive index for controlling light reflection, but having similar chemicals; for example, such as being preferably miscible and/or similar UV curing characteristics.

在本發明之另一具體例中，可製造用於資料傳輸之光學互連，例如積體電路。光學互連基本上是光纖，且可包含以光學互連電子晶片之分級或未分級材料。CMOS亞微米晶片技術中之資料傳輸，會受到透過互連之標準晶載傳輸之限制。晶片對晶片資料傳輸可藉由使用光學互連取代傳統使用的金屬互連而大幅地增加。例如，可使用垂直腔表面發射雷射(VCSEL)作為光學互連。該晶載光源可任擇地透過本發明所述之列印光管或光纖，連接至晶載光檢測器。In another embodiment of the invention, an optical interconnect for data transfer, such as an integrated circuit, can be fabricated. The optical interconnect is essentially an optical fiber and may comprise a graded or ungraded material that optically interconnects the electronic wafer. Data transmission in CMOS sub-micron wafer technology is limited by standard crystal-borne transmission through interconnects. Wafer-to-wafer data transfer can be substantially increased by using optical interconnects instead of traditionally used metal interconnects. For example, vertical cavity surface emitting lasers (VCSELs) can be used as optical interconnects. The crystal carrier light source can optionally be coupled to the on-chip photodetector via a print tube or fiber of the present invention.

本發明之另一具體例是使用材料梯度之平面鏡頭，其具有變曲以及聚光能力。傳統上，鏡片不是平的，且為了使光變曲，其等之形狀需為凸或凹的。會聚光之平面鏡片較佳地包含在邊緣處之相對高的折射率之材料以及在中心處之相對低的折射率之材料。即使鏡片維持平面形狀，此中心低至邊緣高之徑向分級的折射率材料仍會使光變曲。Another embodiment of the present invention is a planar lens using a material gradient having variability and concentrating capabilities. Traditionally, the lens is not flat, and in order to distort the light, its shape needs to be convex or concave. The planar lens that converges preferably comprises a relatively high refractive index material at the edges and a relatively low refractive index material at the center. Even if the lens maintains a planar shape, the radially graded refractive index material having a center as low as the edge will still distort the light.

在本發明之另一具體例中，可列印聲學梯度。分級的聲學纖維，例如，超音波感測器，可用3D互連連接。超音波傳感器較佳地容許聲音傳進組織而不會被反射。例如，可藉由以物理方式製造高密度傳感器(如正溫度係數(PTC)陶瓷)與低密度傳感器(如密度與組織相似之材料)之分級，達到聲學阻抗匹配。 聚合物之電磁輻射固化之替代方案In another embodiment of the invention, the acoustic gradient can be printed. Graded acoustic fibers, such as ultrasonic sensors, can be connected using 3D interconnects. Ultrasonic sensors preferably allow sound to pass into the tissue without being reflected. For example, acoustic impedance matching can be achieved by physically fabricating a high density sensor (such as a positive temperature coefficient (PTC) ceramic) and a low density sensor (such as a material having a density similar to tissue). Alternative to electromagnetic radiation curing of polymers

Aerosol Jet®製造的高縱橫比3D結構，可使用任何快速硬化的材料獲得。快速硬化的材料較佳地具有比混合或溶解之時間短的乾燥時間，t_{乾燥 ＜} t_溶解 。例如，可使用快速蒸發溶劑取代可固化聚合物作為懸浮介質。The high aspect ratio 3D construction made by Aerosol Jet® can be obtained with any fast hardening material. The rapidly hardening material preferably has a drying time that is shorter than the time of mixing or dissolution, _and t _drys . For example, a fast evaporating solvent can be used in place of the curable polymer as a suspending medium.

另一替代方案是擬塑性流體，例如，剪切稀化流體。剪切稀化流體是在施加剪切應變處剪切黏度會減低之流體。透過以下方程式，剪切黏度，ɳ，與施加的剪率相關：其中ɳ是黏度，K是基於材料之常數，ϒ 是施加的剪率，而n是流動行為指數。剪切稀化行為發生在n小於1時。剪切稀化流體在剪切時具較低的黏度(較像液體)，而一旦剪切停止立即變得較黏稠。此黏度之立即改變使其適合使用在此所述之Aerosol Jet®技術來列印高縱橫比3D結構。Another alternative is a pseudoplastic fluid, for example, a shear thinning fluid. The shear thinning fluid is a fluid whose shear viscosity is reduced at the application of shear strain. The shear viscosity, ɳ, is related to the applied shear rate by the following equation: Where ɳ is the viscosity, K is based on the constant of the material, Υ is the applied shear rate, and n is the flow behavior index. The shear thinning behavior occurs when n is less than one. The shear thinning fluid has a lower viscosity (like a liquid) when sheared, and becomes more viscous as soon as the shear stops. This immediate change in viscosity makes it suitable for printing high aspect ratio 3D structures using the Aerosol Jet® technology described herein.

雖然本發明是參考所揭示的具體例來進行詳細的說明，但其它具體例亦可達到相同的結果。本發明之變化以及修飾對熟悉此技藝之人士而言是顯而易見的，且其意圖涵蓋所有此等修飾以及相等物。以上所引述之所有專利以及公開案之完整揭示內容，均在此併入本案以為參考。Although the present invention has been described in detail with reference to the specific examples disclosed, other specific examples can achieve the same results. Variations and modifications of the invention are obvious to those skilled in the art, and are intended to cover all such modifications and equivalents. All patents cited above and the entire disclosure of the disclosure are incorporated herein by reference.

10、11‧‧‧載送氣體10, 11‧‧‧ Carrying gas

12‧‧‧鞘氣12‧‧‧ sheath gas

22‧‧‧沈積頭22‧‧‧Deposition head

24‧‧‧沈積噴嘴24‧‧‧Deposition nozzle

26‧‧‧材料26‧‧‧Materials

27‧‧‧第二材料27‧‧‧Second material

28‧‧‧標的28‧‧‧ Subject

30‧‧‧第一霧化器30‧‧‧First nebulizer

31、33‧‧‧噴霧材料31, 33‧‧‧ spray materials

32‧‧‧第二霧化器32‧‧‧Second atomizer

34‧‧‧混合槽34‧‧‧ mixing tank

36‧‧‧液滴噴射流36‧‧‧Drop jet

37‧‧‧光37‧‧‧Light

50‧‧‧沈積物50‧‧‧Sediment

51‧‧‧懸垂結構51‧‧‧Overhanging structure

60‧‧‧入射光60‧‧‧ incident light

62‧‧‧光纖核心62‧‧‧Fiber core

64、66、68、70、72、74、76‧‧‧濾光器64, 66, 68, 70, 72, 74, 76‧‧‧ filters

78‧‧‧光學護套78‧‧‧Optical sheath

80‧‧‧不同波長之光80‧‧‧Lights of different wavelengths

90、100‧‧‧丙烯酸柱90, 100‧‧‧Acrylic column

92‧‧‧針頭92‧‧‧ needle

所附的圖式，其併入本發明並形成本發明說明書之一部分，舉例說明數個本發明之具體例，且加上說明，用於解釋本發明之原理。該等圖式僅供例示說明本發明之較佳具體例之目的，不能被解釋為本發明之限制。在圖式中： 圖1A是描述噴霧噴射三維列印用於垂直或橫向建立3D結構之機制之示意圖。 圖1B是顯示垂直建立3D結構之更詳細的示意圖。 圖1C是顯示橫向建立3D結構之更詳細的示意圖。 圖2A-2C是依照本發明之具體例列印之聚合物柱陣列之影像。圖2D是顯示柱建造速率之圖。 圖3是複合柱陣列之影像。 圖4A以及4B分別是依照本發明之具體例列印之中介層之透視圖以及頂視圖。 圖5A顯示使用圖1中所示之偏移方法列印之三維似鐵叉(jack-like)結構。圖5B顯示開放錐結構。 圖6A以及6B顯示具有沿著長度之開放內部之封閉通道。圖6C顯示墨水在通道之內部流動。 圖7A以及7B分別顯示具有L形列印柱之個別的天線以及天線之陣列。圖7C以及7D是列印在微晶片上之3D電氣組件之影像。 圖8A顯示列印時藉由傾斜列印頭製得之自立聚合物彈簧。圖8B顯示支撐一塊體之彈簧。 圖9A是顯示銀奈米粒子之光學密度之圖。圖9B顯示用原位照射方法列印之3D銀線陣列。 圖10A-10F是使用UV聚合物以及飛行中固化列印的各種3D形狀之影像。 圖11是本發明用於混合二種具有電磁固化能力之材料之裝置之示意圖。 圖12是列印在針尖上之丙烯酸柱之影像。 圖13A是使用本發明之Aerosol Jet®方法列印在LED晶片上之光管之影像。 圖13B是使用本發明之Aerosol Jet®方法各個列印在LED晶片上之光管陣列之影像。 圖13C是光通過LED晶片上之光管之影像。 圖14是在具有周期性折射率變化的光纖中之選擇性光反射之示意圖。The accompanying drawings, which are incorporated in and in the The drawings are for illustrative purposes only and are not to be construed as limiting. In the drawings: Figure 1A is a schematic diagram depicting the mechanism of spray jet three-dimensional printing for establishing a 3D structure either vertically or laterally. Figure 1B is a more detailed schematic diagram showing the vertical creation of a 3D structure. Figure 1C is a more detailed schematic diagram showing the lateral creation of a 3D structure. 2A-2C are images of a polymer column array printed in accordance with a specific embodiment of the present invention. Figure 2D is a graph showing the column construction rate. Figure 3 is an image of a composite column array. 4A and 4B are respectively a perspective view and a top view of an interposer printed in accordance with a specific example of the present invention. Figure 5A shows a three-dimensional jack-like structure printed using the offset method shown in Figure 1. Figure 5B shows the open cone structure. Figures 6A and 6B show closed channels having an open interior along the length. Figure 6C shows the ink flowing inside the channel. 7A and 7B show an individual antenna having an L-shaped column and an array of antennas, respectively. Figures 7C and 7D are images of 3D electrical components printed on a microchip. Figure 8A shows a self-standing polymer spring made by tilting the print head during printing. Figure 8B shows the spring supporting the body. Figure 9A is a graph showing the optical density of silver nanoparticles. Figure 9B shows a 3D silver line array printed by in situ illumination. Figures 10A-10F are images of various 3D shapes using UV polymers and in-flight cured printing. Figure 11 is a schematic illustration of the apparatus of the present invention for mixing two materials having electromagnetic curing capabilities. Figure 12 is an image of an acrylic column printed on the tip of the needle. Figure 13A is an image of a light pipe printed on an LED wafer using the Aerosol Jet® method of the present invention. Figure 13B is an image of a light pipe array printed on an LED wafer using the Aerosol Jet® method of the present invention. Figure 13C is an image of light passing through a light pipe on an LED wafer. Figure 14 is a schematic illustration of selective light reflection in an optical fiber having a periodic refractive index change.

Claims (18)

一種用於在基材上製造三維結構之方法，該方法包含： 將噴霧液滴從一沉積頭推至該基材上； 部分地改變在飛行中之該等噴霧液滴的特性；以及 當該等噴霧液滴沉積成為該三維結構之一部分時，完全改變其等之特性。A method for making a three-dimensional structure on a substrate, the method comprising: pushing a spray droplet from a deposition head onto the substrate; partially altering characteristics of the spray droplets in flight; and when When the spray droplet deposition becomes part of the three-dimensional structure, its characteristics are completely changed. 如請求項1之方法，其中改變特性包含使用電磁輻射固化或硬化。The method of claim 1, wherein changing the property comprises curing or hardening using electromagnetic radiation. 如請求項2之方法，其中固化包含紫外線(UV)固化。The method of claim 2, wherein the curing comprises ultraviolet (UV) curing. 如請求項2之方法，其中該等噴霧液滴包含光可固化聚合物，且該所製得的三維結構包含經固化的聚合物。The method of claim 2, wherein the spray droplets comprise a photocurable polymer, and the resulting three-dimensional structure comprises a cured polymer. 如請求項4之方法，其中該等噴霧液滴包含分散在該光可固化聚合物中之固態粒子，且所製得的三維結構包含經固化的聚合物，該經固化的聚合物包含經包埋的固態粒子。The method of claim 4, wherein the spray droplets comprise solid particles dispersed in the photocurable polymer, and the resulting three-dimensional structure comprises a cured polymer, the cured polymer comprising a package Buried solid particles. 如請求項5之方法，其中該等固態粒子包含陶瓷、金屬、纖維或矽。The method of claim 5, wherein the solid particles comprise ceramic, metal, fiber or ruthenium. 如請求項1之方法，其中該等噴霧液滴包含溶劑，且改變特性包含使該溶劑蒸發。The method of claim 1, wherein the spray droplets comprise a solvent, and changing the property comprises evaporating the solvent. 如請求項7之方法，其中該等噴霧液滴包含金屬奈米粒子，該方法另外包含： 用UV輻射照射該等噴霧液滴； 加熱該等金屬奈米粒子；以及 充分地加熱該等噴霧液滴以至少部分地使該溶劑蒸發。The method of claim 7, wherein the spray droplets comprise metal nanoparticles, the method additionally comprising: irradiating the spray droplets with UV radiation; heating the metal nanoparticles; and heating the spray liquid sufficiently The dropping is to at least partially evaporate the solvent. 如請求項8之方法，其另外包含在該等金屬奈米粒子經沉積之後持續照射該等金屬奈米粒子，從而至少部份地燒結該等金屬奈米粒子。The method of claim 8, further comprising continuously irradiating the metal nanoparticles after deposition of the metal nanoparticles to at least partially sinter the metal nanoparticles. 如請求項1之方法，其另外包含相對於該基材傾斜或移動該沉積頭。The method of claim 1, further comprising tilting or moving the deposition head relative to the substrate. 如請求項1之方法，其包含在不需要犧牲支撐物或傾斜該沉積頭或該基材之情況下，製造懸垂結構。The method of claim 1, comprising fabricating the overhang structure without sacrificing the support or tilting the deposition head or the substrate. 如請求項1之方法，其中該沉積頭與該基材間之噴射距離(standoff distance)為至少1mm。The method of claim 1, wherein the deposition distance between the deposition head and the substrate is at least 1 mm. 如請求項12之方法，其中該沉積頭與該基材間之噴射距離為至少2mm。The method of claim 12, wherein the deposition distance between the deposition head and the substrate is at least 2 mm. 如請求項1之方法，其包含增加該等噴霧液滴在飛行中之黏度。The method of claim 1, which comprises increasing the viscosity of the spray droplets during flight. 如請求項1之方法，其包含用電磁輻射照射在飛行中之該等噴霧液滴以及在該等噴霧液滴經沉積後之該等噴霧液滴。The method of claim 1, comprising irradiating the spray droplets in flight with electromagnetic radiation and the spray droplets after the spray droplets are deposited. 如請求項15之方法，其包含用電磁輻射從超過一個方向照射在飛行中之該等噴霧液滴。The method of claim 15 which comprises irradiating the spray droplets in flight with more than one direction with electromagnetic radiation. 如請求項1之方法，其包含用電磁輻射加熱在飛行中之該等噴霧液滴以及在該等噴霧液滴經沉積後之該等噴霧液滴。The method of claim 1, comprising heating the spray droplets in flight with electromagnetic radiation and the spray droplets after the spray droplets are deposited. 如請求項1之方法，其中該所製得的三維結構包含選自於由下列所構成之群組之結構：微米量級之表面紋理、機械中介層(mechanical interposer)、精密墊片、包含經包埋的電連接器之機械中介層、封閉中空結構、機械支架以及功能性電線。The method of claim 1, wherein the prepared three-dimensional structure comprises a structure selected from the group consisting of: surface textures on the order of micrometers, mechanical interposers, precision spacers, inclusions Mechanical interposer for embedded electrical connectors, enclosed hollow structures, mechanical supports, and functional wires.