TWI793783B - Supercritical fluids (scfs) treatment of porous silicon structure and method thereof - Google Patents
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本發明係關於一種利用超臨界流體〔Supercritical fluids,SCFs〕處理〔treatment〕多孔矽〔porous silicon〕結構及其方法;再者,特別是關於一種可提升生物相容性〔biocompatibility〕之利用超臨界流體處理多孔矽結構及其方法;再者,更特別是關於一種可提高細包存活率〔cell viability〕之利用超臨界流體增益處理多孔矽結構及其方法。 The present invention relates to a kind of processing (treatment) porous silicon (porous silicon) structure and its method using supercritical fluids (Supercritical fluids, SCFs); Fluid treatment of porous silicon structures and methods thereof; more particularly, a method for treating porous silicon structures with supercritical fluids that can improve cell viability.
舉例而言,習用相關多孔性材料,如中華民國專利公告第TW-I530006號之〝多孔性電活性材料〞發明專利,其揭示一種包括含矽之電活性多孔性顆粒碎塊的組成物。該組成物可用以製造電極材料,而該組成物包含數個多孔性顆粒碎塊,且該多孔性顆粒碎塊為藉由破碎數個含矽之多孔性顆粒而獲得。 For example, related porous materials are commonly used, such as the invention patent of "Porous Electroactive Material" in Patent Publication No. TW-I530006 of the Republic of China, which discloses a composition including silicon-containing electroactive porous particle fragments. The composition can be used to manufacture electrode materials, and the composition includes several porous particle fragments, and the porous particle fragments are obtained by crushing several silicon-containing porous particles.
承上,前述第TW-I530006號之該多孔性顆粒碎塊為含孔洞的多孔性顆粒碎塊,而該多孔性顆粒碎塊包含數個孔洞、數個空穴及數個管道,且數個該管道形成數個網絡,且該孔洞、空穴及管道由顆粒結構之數個含矽的壁進行分隔及界定。 Continuing from the above, the porous particle fragment of the aforementioned TW-I530006 is a porous particle fragment containing holes, and the porous particle fragment contains several holes, several cavities and several channels, and several The channels form networks and the pores, cavities and channels are separated and bounded by silicon-containing walls of the granular structure.
承上,前述第TW-I530006號之該多孔性顆粒碎塊為實質不規則的形狀或表面型態之碎形,其衍生自原始界定或限定衍生出碎形的多孔性顆粒裡之孔洞或孔洞網 絡的矽材料而本身不包括孔洞、管道或是孔洞或管道的網絡。 Continuing from the above, the porous particle fragments of the aforementioned TW-I530006 are fractals of substantially irregular shape or surface type, which are derived from the holes or holes in the porous particles originally defined or defined to derive the fractal shape net A network of silicon materials that does not itself include holes, channels, or a network of holes or channels.
承上,前述第TW-I530006號之該多孔性顆粒碎塊為具有實質不規則的形狀或表面型態之碎形,其衍生自原始界定線性、分支或層狀延長元件之隨機或規則網絡的矽材料,其中一或更多個離散的或交互連接的空穴空間或管道乃界定於網絡的延長元件之間。 Continuing from the above, the porous particle fragments of the aforementioned TW-I530006 are fractals with substantially irregular shape or surface morphology, which are derived from the random or regular network of originally defined linear, branched or layered elongated elements Silicon material in which one or more discrete or interconnected void spaces or channels are defined between elongated elements of the network.
然而,前述專利公告第TW-I530006號專利僅揭示多孔性電活性材料及其含矽的多孔性顆粒碎塊,但其並未揭示如何處理該多孔性電活性材料及其含矽的多孔性顆粒碎塊,因此其必然存在進一步處理其結構、其操作方法及製造方法之潛在需求。 However, the aforementioned patent announcement No. TW-I530006 only discloses fragments of the porous electroactive material and its silicon-containing porous particles, but it does not reveal how to treat the porous electroactive material and its silicon-containing porous particles Fragments, therefore there is necessarily a potential need for further processing of its structure, its method of operation and method of manufacture.
另一習用相關高溫超導體之改質應用,如中華民國專利公告第TW-I542051號之〝高溫超導體〔HTS〕薄膜及其改質或產生方法〞發明專利,其揭示一種高溫超導體薄膜。該高溫超導體薄膜包含具有晶體結構的高溫超導體材料。 Another conventional modification application related to high-temperature superconductors, such as the invention patent of "High Temperature Superconductor (HTS) Thin Film and Its Modification or Production Method" Patent Publication No. TW-I542051 of the Republic of China, discloses a high-temperature superconductor thin film. The high temperature superconductor thin film contains a high temperature superconductor material having a crystal structure.
承上,前述第TW-I542051號之該高溫超導體薄膜包含一第一層及一第二層或一第三層,而該第一層包含一高溫超導體材料,且該第二層包含一改質材料,且該改質材料鍵結於該高溫超導體材料,且該第三層包含一基板材料。 Continuing from the above, the high-temperature superconductor thin film of the aforementioned TW-I542051 includes a first layer and a second layer or a third layer, and the first layer includes a high-temperature superconductor material, and the second layer includes a modified material, and the modified material is bonded to the high temperature superconductor material, and the third layer includes a substrate material.
承上,前述第TW-I542051號之該高溫超導體材料的操作特性在鍵結於該改質材料的該高溫超導體材料具有改良之操作特性,而該改良之操作特性包含較高的轉變溫度,且該改質材料包含鉻、銅、鉍、鈷、釩、鈦、銠、鈹、鎵、硒或其他材料。 Continuing from the above, the operating characteristics of the high-temperature superconductor material of the aforementioned TW-I542051 is that the high-temperature superconductor material bonded to the modified material has improved operating characteristics, and the improved operating characteristics include a higher transition temperature, and The modifying material includes chromium, copper, bismuth, cobalt, vanadium, titanium, rhodium, beryllium, gallium, selenium or other materials.
然而,前述專利公告第TW-I542051號專利僅揭示高溫超導體薄膜、其選擇改質材料及其所改質高溫超 導體材料,但其並未揭示如何改質多孔性矽材料及其改質材料,因此其必然存在進一步提供改質多孔性矽材料結構、其操作方法及製造方法之潛在需求。 However, the aforementioned patent announcement No. TW-I542051 only discloses the high-temperature superconductor thin film, its selected modified material and the modified high-temperature superconductor Conductor material, but it does not disclose how to modify the porous silicon material and the modified material, so there must be a potential demand for further providing the structure of the modified porous silicon material, its operation method and manufacturing method.
另一習用相關超臨界流體之應用,如中華民國專利公告第TW-I606522號之〝利用超臨界流體進行磊晶薄膜剝離方法、其剝離薄膜轉移方法及其構造〞發明專利,其揭示一種利用超臨界流體進行磊晶薄膜剝離方法。該利用超臨界流體進行磊晶薄膜剝離方法包含步驟:首先,於一基板上形成一犧牲層及一磊晶薄膜,而該犧牲層選自砷化鋁,且該磊晶薄膜選自一砷化鎵薄膜或一矽晶薄膜。 Another conventional application of related supercritical fluids, such as the invention patent of "Using Supercritical Fluid to Carry Out Epitaxy Thin Film Stripping Method, Its Stripping Film Transfer Method and Its Structure" No. Critical fluid for epitaxial thin film lift-off method. The epitaxial thin film peeling method using supercritical fluid includes the steps: first, a sacrificial layer and an epitaxial thin film are formed on a substrate, and the sacrificial layer is selected from aluminum arsenide, and the epitaxial thin film is selected from an arsenic gallium thin film or a silicon thin film.
承上,前述第TW-I606522號之該利用超臨界流體進行磊晶薄膜剝離方法另包含步驟:接著,將一蝕刻液混合一超臨界流體,以形成一超臨界流體混合蝕刻液,且該蝕刻液選自氫氟酸;接著,於該基板上利用該超臨界流體混合蝕刻液進行蝕刻該犧牲層,以便自該基板剝離該磊晶薄膜;接著,當蝕刻完成該犧牲層時,獲得一已剝離磊晶薄膜於該基板上。 Continuing from the above, the aforementioned TW-I606522 method for peeling epitaxial thin films using supercritical fluids further includes the following steps: then, mixing an etching solution with a supercritical fluid to form a supercritical fluid mixed etching solution, and the etching The solution is selected from hydrofluoric acid; then, the sacrificial layer is etched on the substrate using the supercritical fluid mixed etching solution, so as to peel off the epitaxial film from the substrate; then, when the sacrificial layer is etched, a peeling off the epitaxial film on the substrate.
另一習用相關超臨界流體之其它應用,例如:中華民國專利公開第TW-200526513號之〝利用超臨界流體/化學配方移除微機電系統〔MEMS〕犧牲層〞發明專利申請案,其揭示一種自其上具有含矽物質之基板移除含矽物質之方法,而該方法包含一SCF基組成物,且該SCF基組成物包含一SCF、至少一共溶劑、至少一蝕刻劑物種及至少一表面活性劑,且依不同需求可選擇包含或不包含該表面活性劑。 Another conventional application of related supercritical fluids, for example: Republic of China Patent Publication No. TW-200526513 "Using Supercritical Fluid/Chemical Formula to Remove Micro-Electro-Mechanical System (MEMS) Sacrificial Layer" patent application, which discloses a Method of removing silicon-containing material from a substrate having silicon-containing material thereon, the method comprising an SCF-based composition comprising an SCF, at least one co-solvent, at least one etchant species, and at least one surface active agent, and can choose to include or not contain the surfactant according to different requirements.
承上,前述第TW-200526513號之該方法將一基板及SCF基組成物在一充分的接觸條件下進行接觸一充分的時間,以便自該基板移除一含矽物質,而該接觸條件可選擇包含在自約1400至約4400psi之範圍內之壓力,且 該接觸時間可選擇在自約30秒至約30分鐘之範圍內,且該含矽物質可選擇為一自由矽、一灰化後殘留物及一蝕刻後殘留物。 Continuing from the above, the method of the aforementioned TW-200526513 contacts a substrate and an SCF-based composition under sufficient contact conditions for a sufficient time to remove a silicon-containing substance from the substrate, and the contact conditions can selecting a pressure comprised in the range from about 1400 to about 4400 psi, and The contact time can be selected to range from about 30 seconds to about 30 minutes, and the silicon-containing species can be selected to be a free silicon, a post-ash residue, and a post-etch residue.
承上,前述第TW-200526513號之該SCF選自二氧化碳、氧、氬、氪、氙或氨,而該共溶劑包含至少一C1-C6醇、甲醇或異丙醇,且該含矽物質選自由氧化矽或氮化矽,且該蝕刻劑物種包含二氟化銨或XeF2,且該表面活性劑包含至少一非離子或陰離子表面活性劑。 As above, the SCF of the aforementioned TW-200526513 is selected from carbon dioxide, oxygen, argon, krypton, xenon or ammonia, and the co-solvent contains at least one C1-C6 alcohol, methanol or isopropanol, and the silicon-containing substance is selected from Free silicon oxide or silicon nitride, and the etchant species include ammonium difluoride or XeF 2 , and the surfactant includes at least one nonionic or anionic surfactant.
另一習用相關超臨界流體之其它應用,例如:中華民國專利公開第TW-201227802號之〝具易移除犧牲層的磊晶結構及其製造方法〞發明專利申請案,其揭示一種具易移除犧牲層的磊晶結構的製造方法包含:製備一第一基板。 Another conventional application of related supercritical fluids, for example: Patent Publication No. TW-201227802 of the Republic of China "Epitaxy structure with easy-to-remove sacrificial layer and its manufacturing method" patent application, which discloses an easily-removable sacrificial layer The manufacturing method of the epitaxial structure except the sacrificial layer includes: preparing a first substrate.
承上,前述第TW-201227802號之該製造方法包含:於該第一基板上形成一氧化鎵犧牲層,而該氧化鎵犧牲層滿足GaOx,其中0.5≦x≦3.5;於該氧化鎵犧牲層上磊晶成長形成一磊晶結構層。另外,在該步驟之間包含:將該氧化鎵犧牲層進行圖案化。 As mentioned above, the manufacturing method of the aforementioned TW-201227802 includes: forming a gallium oxide sacrificial layer on the first substrate, and the gallium oxide sacrificial layer satisfies GaO x , wherein 0.5≦x≦3.5; Epitaxial growth on the layer forms an epitaxial structure layer. In addition, between the steps includes: patterning the gallium oxide sacrificial layer.
承上,前述第TW-201227802號之該製造方法包含:於該磊晶結構層上形成一第二基板;通入一蝕刻液將該氧化鎵犧牲層移除,以便將該磊晶結構層與第一基板之間產生互相分離。 Based on the above, the manufacturing method of the aforementioned TW-201227802 includes: forming a second substrate on the epitaxial structure layer; passing through an etching solution to remove the gallium oxide sacrificial layer, so that the epitaxial structure layer and The first substrates are separated from each other.
另一習用相關超臨界流體之其它應用,例如:美國專利第US-8071458號之〝Method for forming an interfacial passivation layer on the Ge semiconductor〞發明專利,其揭示一種形成鍺半導體表面保護層的方法。該形成鍺半導體表面保護層的方法包含步驟:首先,於一矽晶圓上進行磊晶製程,以形成一磊晶鍺半導體層;接著,再形成一二氧化矽層於該磊晶鍺半導體層上,以做為一閘極介 電絕緣膜。 Another conventional application of related supercritical fluids, for example: US Patent No. US-8071458 "Method for forming an interfacial passivation layer on the Ge semiconductor" invention patent, which discloses a method for forming a germanium semiconductor surface protection layer. The method for forming a germanium semiconductor surface protection layer comprises steps: firstly, performing an epitaxial process on a silicon wafer to form an epitaxial germanium semiconductor layer; then, forming a silicon dioxide layer on the epitaxial germanium semiconductor layer on, as a gate interposer electrical insulating film.
承上,前述第US-8071458號之該形成鍺半導體表面保護層的方法另包含步驟:接著,通入一超臨界流體至該二氧化矽層及磊晶鍺半導體層的界面,使該界面形成一界面保護層;接著,形成一鋁薄膜於該二氧化矽層上,以形成為一金氧半導體電容器的一上電極,且以該熱蒸鍍法形成該鋁薄膜於該磊晶鍺半導體層的底部,以做為該金氧半導體電容器的一下電極。 Continuing from the above, the method for forming a germanium semiconductor surface protective layer in the aforementioned US-8071458 further includes a step: then, passing a supercritical fluid to the interface between the silicon dioxide layer and the epitaxial germanium semiconductor layer, so that the interface is formed An interface protection layer; then, forming an aluminum film on the silicon dioxide layer to form an upper electrode of a metal oxide semiconductor capacitor, and forming the aluminum film on the epitaxial germanium semiconductor layer by the thermal evaporation method The bottom of the metal oxide semiconductor capacitor is used as the lower electrode.
承上,前述第US-8071458號於該二氧化矽層及磊晶鍺半導體層之間的界面上僅利用通入該超臨界流體,以便形成該界面保護層,以保護該磊晶鍺半導體層之表面。顯然,前述第US-8071458號並未揭示如何採用超臨界流體輔助於蝕刻液,以輔助進行其磊晶薄膜剝離作業或轉移作業。 As mentioned above, the aforementioned US-8071458 only uses the supercritical fluid to form the interface protection layer on the interface between the silicon dioxide layer and the epitaxial germanium semiconductor layer to protect the epitaxial germanium semiconductor layer. the surface. Apparently, the above-mentioned US-8071458 does not disclose how to use supercritical fluid to assist the etchant to assist in the stripping or transferring of the epitaxial film.
然而,雖然前述專利公告第TW-I606522號專利揭示利用超臨界流體進行磊晶薄膜剝離方法、專利公開第TW-200526513號揭示利用超臨界流體/化學配方移除微機電系統犧牲層、專利公開第TW-201227802號揭示具易移除犧牲層的磊晶結構及其製造方法及美國第US-8071458號揭示形成鍺半導體表面保護層的方法之各種超臨界流體應用,但其並未揭示如何處理多孔性矽材料及其處理材料,因此其必然存在進一步提供處理多孔性矽材料結構、其操作方法及製造方法之潛在需求。 However, although the aforementioned Patent Publication No. TW-I606522 discloses a method for peeling epitaxial thin films using supercritical fluids, Patent Publication No. TW-200526513 discloses the use of supercritical fluid/chemical formulations to remove MEMS sacrificial layers, and Patent Publication No. TW-201227802 discloses an epitaxial structure with an easy-to-remove sacrificial layer and its manufacturing method, and US-8071458 discloses the application of various supercritical fluids to the method of forming a germanium semiconductor surface protection layer, but it does not disclose how to deal with porous Porous silicon materials and their processing materials, so there must be a potential demand for further providing processing porous silicon material structures, its operating methods and manufacturing methods.
顯然,前述中華民國專利公告第TW-I530006號、專利公告第TW-I542051號、專利公告第TW-I606522號、專利公開第TW-200526513號、專利公開第TW-201227802號及美國第US-8071458號專利及專利申請案僅為本發明技術背景之參考及說明目前技術發展狀態而已,其並非用以限制本發明之範圍。 Obviously, the aforementioned ROC Patent Announcement No. TW-I530006, Patent Announcement No. TW-I542051, Patent Announcement No. TW-I606522, Patent Publication No. TW-200526513, Patent Publication No. TW-201227802 and U.S. No. US-8071458 The No. patent and patent application are only for reference of the technical background of the present invention and to illustrate the current state of technological development, and are not intended to limit the scope of the present invention.
有鑑於此,本發明為了滿足上述技術問題及需求,其提供一種利用超臨界流體處理多孔矽結構及其方法,其在一矽基板上以一蝕刻方法進行蝕刻,以便形成一具多孔矽結構之基板,並將該具多孔矽結構之基板以一超臨界流體進行超臨界流體處理,以便獲得一已處理多孔矽基板,且於該已處理多孔矽基板上適當形成數個已處理多孔結構,且將至少一細胞株可選擇結合於該已處理多孔矽基板之數個已處理多孔結構,且於該已處理多孔矽基板上進行栽培該細胞株,以便獲得一已培養細胞株,並提高〔或增進〕其細胞存活率,因此相對於習用多孔矽基板可大幅提升其表面化學活性、提供細胞相容性及細胞生存率。 In view of this, in order to meet the above-mentioned technical problems and needs, the present invention provides a method for treating porous silicon structures with supercritical fluids, which etches a silicon substrate with an etching method to form a porous silicon structure. substrate, and subjecting the substrate with a porous silicon structure to supercritical fluid treatment with a supercritical fluid, so as to obtain a processed porous silicon substrate, and appropriately form several processed porous structures on the processed porous silicon substrate, and At least one cell strain can be selectively combined with several treated porous structures of the treated porous silicon substrate, and the cell strain is cultivated on the treated porous silicon substrate, so as to obtain a cultured cell strain, and improve [or Improve] its cell survival rate, so compared with the conventional porous silicon substrate, it can greatly improve its surface chemical activity, provide cell compatibility and cell survival rate.
本發明之主要目的係提供一種利用超臨界流體處理多孔矽結構及其方法,其在一矽基板上以一蝕刻方法進行蝕刻,以便形成一具多孔矽結構之基板,並將該具多孔矽結構之基板以一超臨界流體進行超臨界流體處理,以便獲得一已處理多孔矽基板,且於該已處理多孔矽基板上適當形成數個已處理多孔結構,且將至少一細胞株可選擇結合於該已處理多孔矽基板之數個已處理多孔結構,且於該已處理多孔矽基板上進行栽培該細胞株,以便獲得一已培養細胞株,並提高〔或增進〕其細胞存活率,以達成可提升其表面化學活性、提供細胞相容性及細胞生存率之目的及功效。 The main purpose of the present invention is to provide a kind of processing porous silicon structure and its method by utilizing supercritical fluid, it etches with an etching method on a silicon substrate, so that form the substrate of a porous silicon structure, and this porous silicon structure The substrate is subjected to supercritical fluid treatment with a supercritical fluid, so as to obtain a processed porous silicon substrate, and several processed porous structures are appropriately formed on the processed porous silicon substrate, and at least one cell line can be selectively combined in Several treated porous structures of the treated porous silicon substrate, and the cell strain is cultivated on the treated porous silicon substrate, so as to obtain a cultured cell strain, and increase (or enhance) its cell survival rate, so as to achieve It can enhance its surface chemical activity, improve the purpose and effect of cytocompatibility and cell viability.
為了達成上述目的,本發明較佳實施例之利用超臨界流體處理多孔矽結構包含: In order to achieve the above objectives, the processing of porous silicon structures using supercritical fluids in a preferred embodiment of the present invention includes:
一矽基板,其由一含矽材料製成; a silicon substrate made of a silicon-containing material;
一具多孔矽結構之基板,其在該矽基板上以一蝕刻方法進行蝕刻,以便形成該具多孔矽結構之基板; A substrate with a porous silicon structure, which is etched on the silicon substrate by an etching method to form the substrate with a porous silicon structure;
至少一超臨界流體,其將該具多孔矽結構之基板以 該超臨界流體進行超臨界流體處理,以便獲得一已處理多孔矽基板; At least one supercritical fluid, which will have the substrate with porous silicon structure The supercritical fluid is subjected to supercritical fluid treatment in order to obtain a treated porous silicon substrate;
數個已處理多孔結構,其形成於該已處理多孔矽基板上;及 a plurality of treated porous structures formed on the treated porous silicon substrate; and
至少一已培養細胞株,其將至少一細胞株可選擇結合於該已處理多孔矽基板之數個已處理多孔結構; at least one cultured cell strain, which selectively binds at least one cell strain to several treated porous structures of the treated porous silicon substrate;
其中於該已處理多孔矽基板上進行栽培該細胞株,以便獲得一已培養細胞株,並提高〔或增進〕其細胞存活率。 The cell strain is cultivated on the treated porous silicon substrate, so as to obtain a cultured cell strain and increase (or enhance) its cell survival rate.
本發明較佳實施例之該具多孔矽結構之基板形成一微奈米結構。 The substrate with a porous silicon structure in a preferred embodiment of the present invention forms a micro-nano structure.
本發明較佳實施例之該超臨界流體選自二氧化碳超臨界流體。 The supercritical fluid in a preferred embodiment of the present invention is selected from carbon dioxide supercritical fluid.
本發明較佳實施例之該已處理多孔矽基板具有一矽氧碳化物〔SiOC〕。 The processed porous silicon substrate of the preferred embodiment of the present invention has a silicon oxide carbide [SiOC].
本發明較佳實施例之該已處理多孔矽基板之已處理多孔結構具有數個已擴大孔徑。 The processed porous structure of the processed porous silicon substrate in a preferred embodiment of the present invention has several enlarged pore diameters.
為了達成上述目的,本發明較佳實施例之利用超臨界流體處理多孔矽結構方法包含: In order to achieve the above purpose, the method of using supercritical fluid to treat porous silicon structure in a preferred embodiment of the present invention includes:
在一矽基板上以一蝕刻方法進行蝕刻,以便形成一具多孔矽結構之基板; Etching by an etching method on a silicon substrate to form a substrate with a porous silicon structure;
將該具多孔矽結構之基板以一超臨界流體進行超臨界流體處理,以便獲得一已處理多孔矽基板,且於該已處理多孔矽基板上適當形成數個已處理多孔結構; Treating the substrate with the porous silicon structure with a supercritical fluid to obtain a processed porous silicon substrate, and appropriately forming several processed porous structures on the processed porous silicon substrate;
將至少一細胞株可選擇結合於該已處理多孔矽基板之數個已處理多孔結構;及 optionally binding at least one cell line to the treated porous structures of the treated porous silicon substrate; and
於該已處理多孔矽基板上進行栽培該細胞株,以便獲得一已培養細胞株,並提高〔或增進〕其細胞存活率。 Cultivate the cell line on the treated porous silicon substrate, so as to obtain a cultured cell line, and improve (or enhance) its cell survival rate.
本發明較佳實施例之該超臨界流體選自二氧 化碳超臨界流體,並選擇壓力約3000psi或溫度約150℃進行處理作業。 The supercritical fluid of the preferred embodiment of the present invention is selected from the group consisting of dioxygen Carburize supercritical fluid, and choose a pressure of about 3000psi or a temperature of about 150°C for processing operations.
本發明較佳實施例之該超臨界流體添加結合一共溶劑。 The supercritical fluid addition of a preferred embodiment of the present invention incorporates a co-solvent.
本發明較佳實施例之該共溶劑選自水、丙酮或其任意組合體。 The co-solvent of the preferred embodiment of the present invention is selected from water, acetone or any combination thereof.
本發明較佳實施例之該細胞株選自H9c2細胞株或其它細胞株。 The cell strain in a preferred embodiment of the present invention is selected from H9c2 cell strain or other cell strains.
1:矽基板 1: Silicon substrate
10:具多孔矽結構之基板 10: Substrate with porous silicon structure
11:已處理多孔矽基板 11: Processed porous silicon substrate
110:已處理多孔結構 110: processed porous structure
2:蝕刻材料 2: Etching material
3:超臨界流體 3: supercritical fluid
4:細胞株 4: cell line
40:已培養細胞株 40: Cultured cell lines
a:已擴大孔徑 a: enlarged aperture
第1圖:本發明較佳實施例之利用超臨界流體處理多孔矽結構之方塊示意圖。 Figure 1: A schematic block diagram of treating a porous silicon structure with a supercritical fluid according to a preferred embodiment of the present invention.
第2圖:本發明較佳實施例之利用超臨界流體處理多孔矽結構方法之流程示意圖。 Fig. 2: A schematic flow chart of a method for treating a porous silicon structure using a supercritical fluid according to a preferred embodiment of the present invention.
第3圖:本發明較佳實施例之利用超臨界流體處理多孔矽結構於樣品1至6之掃描電子顯微鏡上視影像之示意照片。
Fig. 3: Schematic photographs of
第4圖:本發明較佳實施例之利用超臨界流體處理多孔矽結構於樣品1至6之掃描電子顯微鏡側視影像之示意照片。
Fig. 4: Schematic photographs of scanning electron microscope side-view images of
第5圖:本發明較佳實施例之利用超臨界流體處理多孔矽結構於樣品1至6處理後之原子比例之比較示意圖。
Fig. 5: Schematic diagram comparing the atomic proportions of
第6圖:本發明較佳實施例之利用超臨界流體處理多孔矽結構於樣品1至6處理後進行水滴接觸角量測結果之比較示意圖。
Fig. 6: Schematic diagram comparing the measurement results of the water droplet contact angle after processing the porous silicon structure with supercritical fluid in the preferred embodiment of the present invention after the treatment of
第7圖:本發明較佳實施例之利用超臨界流體處理多孔矽結構於樣品1至6處理後之表面孔徑大小之比較示意圖。
Fig. 7: Schematic diagram comparing surface pore sizes of
第8圖:本發明另一較佳實施例之利用超臨界流體處理 多孔矽結構應用於生物相容性之方塊示意圖。 Figure 8: Another preferred embodiment of the present invention using supercritical fluid treatment Schematic diagram of porous silicon structure applied to biocompatibility.
第9a圖:本發明另一較佳實施例之利用超臨界流體處理多孔矽結構於樣品上培養細胞株之光學顯微鏡影像之示意照片。 Figure 9a: A schematic photo of an optical microscope image of a cell line cultured on a sample using a supercritical fluid to treat a porous silicon structure in another preferred embodiment of the present invention.
第9b圖:本發明另一較佳實施例之利用超臨界流體處理多孔矽結構於樣品上獲得已培養細胞單體之光學顯微鏡螢光影像之示意照片。 Fig. 9b: A schematic photo of an optical microscope fluorescent image of a cultured cell monomer obtained on a sample by using a supercritical fluid to treat a porous silicon structure in another preferred embodiment of the present invention.
第9c圖:本發明另一較佳實施例之利用超臨界流體處理多孔矽結構於樣品上獲得已培養細胞聚合體之光學顯微鏡螢光影像之示意照片。 Fig. 9c: Another preferred embodiment of the present invention is a schematic photo of an optical microscope fluorescence image of a cultured cell aggregate obtained on a sample by using a supercritical fluid to treat a porous silicon structure.
第9d圖:本發明另一較佳實施例之利用超臨界流體處理多孔矽結構於樣品上獲得已培養細胞單體及聚合體之光學顯微鏡疊圖螢光影像之示意照片。 Fig. 9d: Another preferred embodiment of the present invention is a schematic photo of supercritical fluid treatment of a porous silicon structure on a sample to obtain an optical microscope superimposed fluorescent image of cultured cell monomers and aggregates.
為了充分瞭解本發明,於下文將舉例較佳實施例並配合所附圖式作詳細說明,且其並非用以限定本發明。 In order to fully understand the present invention, preferred embodiments will be described below in detail together with the accompanying drawings, which are not intended to limit the present invention.
本發明較佳實施例之利用超臨界流體增益處理多孔矽結構及其方法選擇採用各種超臨界流體,例如:可選擇二氧化碳超臨界流體或其它可能物質的超臨界流體〔例如:氧、氬、氪、氙、氨或其它超臨界流體〕,但其並非用以限制本發明之範圍。 The preferred embodiment of the present invention utilizes supercritical fluids to increase the processing of porous silicon structures and methods thereof. Various supercritical fluids are used, for example: supercritical fluids such as carbon dioxide supercritical fluid or other possible substances can be selected [for example: oxygen, argon, krypton , xenon, ammonia or other supercritical fluids], but it is not intended to limit the scope of the present invention.
承上,本發明較佳實施例之利用超臨界流體增益處理多孔矽結構及其方法可選擇廣泛應用於各種產業,例如:光電產業〔optoelectronic industry〕、微光學產業〔micro-optical industry〕、能量轉換產業〔energy conversion industry〕、環境監測產業〔environment monitoring industry〕、微電子產業〔microelectronic industry〕、半導體晶圓產業〔silicon wafer industry〕、微加工產業〔micromachining industry〕、生物科技產業 〔biotechnical industry〕或生醫產業〔biomedical industry〕,但其並非用以限制本發明之應用範圍。 Continuing from the above, the use of supercritical fluid gain processing porous silicon structure and its method in the preferred embodiment of the present invention can be widely used in various industries, such as: optoelectronic industry [optoelectronic industry], micro-optical industry [micro-optical industry], energy Conversion industry (energy conversion industry), environmental monitoring industry (environment monitoring industry), microelectronics industry (microelectronic industry), semiconductor wafer industry (silicon wafer industry), micromachining industry (micromachining industry), biotechnology industry [biotechnical industry] or biomedical industry [biomedical industry], but it is not intended to limit the scope of application of the present invention.
承上,本發明較佳實施例之利用超臨界流體增益處理多孔矽結構及其方法可選擇適當應用於各種生物相容性之用途及其材料,且其可選擇適當應用於各種人類細胞或動物細胞之各種可能的應用,但其並非用以限制本發明之應用範圍。 Continuing from the above, the use of supercritical fluids in the preferred embodiments of the present invention to gain treatment of porous silicon structures and methods thereof can be appropriately selected for various biocompatible purposes and materials, and it can be appropriately selected for various human cells or animals Various possible applications of cells, but it is not intended to limit the scope of application of the present invention.
第1圖揭示本發明較佳實施例之利用超臨界流體處理多孔矽結構之示意圖。請參照第1圖所示,本發明較佳實施例之利用超臨界流體處理多孔矽結構適用處理加工於一矽基板1上,而該矽基板1可選擇由一含矽材料或其類似成份材料適當製成,且在處理作業前適當清洗〔例如:超音波清洗〕該矽基板1。
FIG. 1 shows a schematic diagram of a preferred embodiment of the present invention for treating porous silicon structures with supercritical fluids. Please refer to Figure 1, the preferred embodiment of the present invention uses supercritical fluid to process the porous silicon structure and is suitable for processing on a
請再參照第1圖所示,舉例而言,該矽基板1可選擇具有一預定尺寸規格〔例如:長度、寬度及厚度〕,而該矽基板1可選擇具有一預定形狀體或一預定形狀基板片體〔例如:長方片體、正方片體、橢圓片體、正圓片體或其它適當形狀片體〕。
Please refer to Figure 1 again, for example, the
第2圖揭示本發明較佳實施例之利用超臨界流體處理多孔矽結構方法之流程示意圖。請參照第1及2圖所示,舉例而言,本發明較佳實施例之利用超臨界流體處理多孔矽結構方法包含步驟S1:首先,以適當技術手段在該矽基板1上可選擇以至少一蝕刻方法,並可選擇一蝕刻材料2進行適當蝕刻〔etching〕,以便適當形成一具多孔矽結構〔porous-structured〕之基板10,即形成已蝕刻矽基板。
FIG. 2 shows a schematic flow chart of a method for treating a porous silicon structure using a supercritical fluid according to a preferred embodiment of the present invention. Please refer to Figures 1 and 2. For example, the method for treating porous silicon structures with supercritical fluids according to a preferred embodiment of the present invention includes step S1: first, select at least An etching method, and an
請再參照第1及2圖所示,舉例而言,依該矽基板1之各種不同參雜濃度或各種不同蝕刻條件〔例如:蝕刻液濃度、蝕刻電流或其它〕,該具多孔矽結構之基板
10可選擇具有各種孔洞大小、各種孔洞型態及各種多孔層厚度等之差異。
Please refer to Figures 1 and 2 again. For example, according to various doping concentrations of the
請再參照第1及2圖所示,舉例而言,在蝕刻完成後,將該具多孔矽結構之基板10進行適當清洗〔例如:酒精沖洗〕,並將該具多孔矽結構之基板10進行適當乾燥〔例如:置於真空球內進行真空乾燥〕,以便進行後續處理作業。
Please refer to Figures 1 and 2 again. For example, after the etching is completed, the
請再參照第1及2圖所示,舉例而言,本發明較佳實施例之利用超臨界流體處理多孔矽結構方法包含步驟S2:接著,以適當技術手段將該具多孔矽結構之基板10以一超臨界流體3進行超臨界流體處理,以便獲得一已處理多孔矽基板11,且於該已處理多孔矽基板11上適當形成數個已處理多孔結構110。
Please refer to Figures 1 and 2 again. For example, the method for treating a porous silicon structure with a supercritical fluid according to a preferred embodiment of the present invention includes step S2: Then, the
請再參照第1及2圖所示,舉例而言,該超臨界流體3選自二氧化碳超臨界流體,並可選擇壓力約3000psi或其它壓力值〔例如:低於3000psi或高於3000psi〕進行處理作業,且可選擇溫度約150℃或其它溫度值〔例如:低於150℃或高於150℃〕進行處理作業一預定時間〔例如:約3小時或其它作業時間〕。
Please refer to Figures 1 and 2 again. For example, the
請再參照第1及2圖所示,舉例而言,本發明另一較佳實施例之該超臨界流體3可選擇添加結合一共溶劑〔co-solvent〕,以便輔助進行處理作業,且該共溶劑選自水、丙酮〔Acetone〕或其任意組合體,例如:該共溶劑僅選自水〔例如:約3ml〕,或該共溶劑可選自水〔例如:約3ml〕及丙酮〔例如:約3ml〕之組合,並獲得各種不同處理效果。
Please refer to Figures 1 and 2 again. For example, the
請再參照第1及2圖所示,舉例而言,該已處理多孔矽基板11之已處理多孔結構110具有數個已擴大孔徑a,且經由不同的該共溶劑〔例如:水、丙酮或其任意組
合體〕於該已處理多孔矽基板11之已處理多孔結構110上可獲得各種不同處理效果。
Please refer to Figures 1 and 2 again, for example, the processed
請再參照第1及2圖所示,舉例而言,該已處理多孔矽基板11及其已處理多孔結構110可選擇應用於各種產業用途,例如:光電產業、微光學產業、能量轉換產業、環境監測產業、微電子產業、半導體晶圓產業、微加工產業、生物科技產業、生醫產業或其相關產業。
Please refer to Figures 1 and 2 again. For example, the processed
請再參照第1及2圖所示,舉例而言,該超臨界流體3可選自二氧化碳超臨界流體〔scCO2〕或其它適當超臨界流體。另外,該已處理多孔矽基板11及其已處理多孔結構110具有一矽氧碳化物〔SiOC〕或其相關化合物。
Please refer to Figures 1 and 2 again. For example, the
請再參照第1及2圖所示,舉例而言,該已處理多孔矽基板11及其已處理多孔結構110可形成一微奈米結構〔microstructure〕,並於該已處理多孔矽基板11及其已處理多孔結構110可改變其表面的化學活性〔chemical activity〕,且該微奈米結構包含數個奈米晶柱〔nano-scale crystal pillar〕。
Please refer to Figures 1 and 2 again, for example, the processed
第3圖揭示本發明較佳實施例之利用超臨界流體處理多孔矽結構於樣品1至6之掃描電子顯微鏡〔SEM,Scanning Electron Microscope〕上視影像之示意照片。第4圖揭示本發明較佳實施例之利用超臨界流體處理多孔矽結構於樣品1至6之掃描電子顯微鏡側視影像之示意照片,其對應於第3圖。請參照第3及4圖所示,舉例而言,本發明較佳實施例採用樣品1至6之厚度皆為約4μm。
Fig. 3 discloses a schematic photograph of images viewed on a scanning electron microscope (SEM, Scanning Electron Microscope) of
第5圖揭示本發明較佳實施例之利用超臨界流體處理多孔矽結構於樣品1至6處理後之原子比例之比較示意圖。請參照第5圖所示,舉例而言,本發明較佳實施例採用樣品1至6獲得經能量色散X-射線光譜〔EDS,
Energy-dispersive X-ray spectroscopy〕分析結果,其顯示樣品1至6之成分比例皆有改變。
Fig. 5 shows a comparison diagram of atomic proportions of
請再參照第5圖所示,舉例而言,相對於樣品1,樣品2至6之氧和碳比例皆提高;相對於未處理的多孔矽樣品2,已處理的樣品3至6之含氧比例皆提高,且其含碳比例則降低,其顯示二氧化碳超臨界流體處理可能有助於形成生物相容性優異的碳氧化矽。
Please refer to Figure 5 again. For example, compared to
第6圖揭示本發明較佳實施例之利用超臨界流體處理多孔矽結構於樣品1至6處理後進行水滴接觸角量測結果之比較示意圖。請參照第6圖所示,舉例而言,本發明較佳實施例採用純水滴與樣品1至6之上表面之間獲得接觸角量測結果,並據此用以判定是否改變其疏水性或親水性。
Fig. 6 shows a comparative schematic diagram of the measurement results of water droplet contact angle after treatment of
請再參照第6圖所示,舉例而言,矽基板在進行蝕刻後其表面更具疏水性,並在進行處理後僅有樣品3及4之表面具有相對較佳親水性,其中樣品3之差異特別明顯,而其餘樣品則處理前後之其疏水性或親水性之改變並不明顯。
Please refer to Figure 6 again. For example, the surface of the silicon substrate is more hydrophobic after etching, and only the surfaces of
第7圖揭示本發明較佳實施例之利用超臨界流體處理多孔矽結構於樣品1至6處理後之比表面積〔單位質量上表面積大小〕之比較示意圖。請參照第7圖所示,舉例而言,本發明較佳實施例採用樣品1至6經軟體計算後之比表面積結果。
Fig. 7 shows a comparative schematic diagram of the specific surface area (surface area per unit mass) of
請再參照第7圖所示,舉例而言,矽基板在進行蝕刻後其比表面積上升,並在進行處理後更進一步產生顯著上升幅度,其中樣品5之比表面積值最高,其顯示處理可使其比表面積進一步上升。
Please refer to Figure 7 again. For example, the specific surface area of the silicon substrate increases after etching, and further increases significantly after treatment. Among them, the specific surface area of
請再參照第7圖所示,舉例而言,在比較樣品4、5及6上,其顯示二氧化碳超臨界流體處理中,採用共
溶劑之適當添加有效提升其處理後比表面積總值,其中將水、丙酮或其組合皆可選擇做為超臨界流體處理中輔助增加比表面積之共溶劑。
Please refer to Fig. 7 again. For example, on
第8圖揭示本發明另一較佳實施例之利用超臨界流體處理多孔矽結構應用於生物相容性之方塊示意圖。請參照第1、2及8圖所示,舉例而言,本發明較佳實施例之利用超臨界流體處理多孔矽結構將該已處理多孔矽基板11及其已處理多孔結構110可選擇應用於生物相容性之用途。
FIG. 8 shows a schematic block diagram of another preferred embodiment of the present invention for treating porous silicon structures with supercritical fluids for biocompatibility. Please refer to Figures 1, 2 and 8, for example, the preferred embodiment of the present invention uses supercritical fluid to process porous silicon structures. The processed
請再參照第1、2及8圖所示,舉例而言,本發明另一較佳實施例之利用超臨界流體處理多孔矽結構方法包含步驟S11:接著,以適當技術手段將至少一細胞株4可選擇結合於該已處理多孔矽基板11之數個已處理多孔結構110。
Please refer to Figures 1, 2 and 8 again. For example, another preferred embodiment of the present invention uses a supercritical fluid to treat porous silicon structures. The method includes step S11: then, at least one cell line is separated by appropriate technical means. 4. Several processed
請再參照第1、2及8圖所示,舉例而言,本發明另一較佳實施例之利用超臨界流體處理多孔矽結構方法包含步驟S12:接著,以適當技術手段於該已處理多孔矽基板11之數個已處理多孔結構110上進行栽培該細胞株,以便獲得至少一已培養細胞株40,且該細胞株4可選自H9c2細胞株〔一種大鼠心肌細胞〕或其它細胞株,並提高〔或增進〕其細胞存活率。
Please refer to Figures 1, 2 and 8 again. For example, another preferred embodiment of the present invention uses supercritical fluid to treat porous silicon structures. Cultivate the cell strain on several processed
第9a圖揭示本發明另一較佳實施例之利用超臨界流體處理多孔矽結構於樣品上培養細胞株之光學顯微鏡〔OM,Optical Microscope〕影像之示意照片〔即真實照片〕。請參照第1、2、8及9a圖所示,舉例而言,本發明較佳實施例可選擇採用一樣品為該已處理多孔矽基板11,並於該樣品上該細胞株4之細胞生存力。
Fig. 9a discloses a schematic photo (that is, a real photo) of an optical microscope (OM, Optical Microscope) image of another preferred embodiment of the present invention using a supercritical fluid to treat a porous silicon structure to culture a cell line on a sample. Please refer to Figures 1, 2, 8 and 9a, for example, a preferred embodiment of the present invention can choose to adopt a sample as the processed
第9b圖揭示本發明另一較佳實施例之利用超臨界流體處理多孔矽結構於樣品上獲得已培養細胞單體之
光學顯微鏡螢光影像〔fluorescence image〕之示意照片。請參照第1、2、8及9b圖所示,舉例而言,本發明較佳實施例可選擇採用一種DNA螢光染色劑〔例如:JC-1或其它螢光染色劑〕進行染色該樣品,並以細胞〔例如:H9c2〕單體〔monomer〕染色後整體吸光率分析於該已處理多孔矽基板11上該細胞株4之細胞生存力。
Figure 9b discloses another preferred embodiment of the present invention using supercritical fluid to process porous silicon structures to obtain cultured cell monomers on samples
Schematic photo of the fluorescence image of an optical microscope. Please refer to Figures 1, 2, 8 and 9b, for example, a preferred embodiment of the present invention can choose to use a DNA fluorescent stain [for example: JC-1 or other fluorescent stains] to stain the sample , and analyze the cell viability of the
第9c圖揭示本發明另一較佳實施例之利用超臨界流體處理多孔矽結構於樣品上獲得已培養細胞聚合體之光學顯微鏡螢光影像之示意照片。請參照第1、2、8及9b圖所示,舉例而言,本發明較佳實施例可選擇以細胞聚合體〔aggregate〕染色後整體吸光率分析於該已處理多孔矽基板11上該細胞株4之細胞生存力。
Fig. 9c discloses a schematic photo of another preferred embodiment of the present invention using a supercritical fluid to treat a porous silicon structure on a sample to obtain an optical microscope fluorescence image of a cultured cell aggregate. Please refer to Figures 1, 2, 8 and 9b. For example, in a preferred embodiment of the present invention, the cells on the treated
第9d圖揭示本發明另一較佳實施例之利用超臨界流體處理多孔矽結構於樣品上獲得已培養細胞單體及聚合體之光學顯微鏡疊圖螢光影像之示意照片。請再參照第9d圖所示,舉例而言,本發明較佳實施例選擇將該樣品之細胞單體及聚合體之光學顯微鏡疊圖螢光影像顯示經二氧化碳超臨界流體處理之樣品具有細胞生存力。 Fig. 9d shows a schematic photo of another preferred embodiment of the present invention using a supercritical fluid to treat a porous silicon structure on a sample to obtain an optical microscope superimposed fluorescent image of cultured cell monomers and aggregates. Please refer to Figure 9d again. For example, the preferred embodiment of the present invention chooses the optical microscope overlay fluorescent image of the cell monomers and aggregates of the sample to show that the sample treated with carbon dioxide supercritical fluid has cell survival force.
請再參照第9a、9b、9c及9d圖所示,舉例而言,本發明較佳實施例選擇採用儀器初步分析的結果顯示經二氧化碳超臨界流體處理之樣品細胞生存力大於以氧電漿處理的樣品,因此可認定二氧化碳超臨界流體處理具有提高H9c2細胞生存力的趨勢。 Please refer to Figures 9a, 9b, 9c and 9d again. For example, the preferred embodiment of the present invention chooses to use the instrument for preliminary analysis. The result of the preliminary analysis shows that the cell viability of the sample treated with carbon dioxide supercritical fluid is greater than that treated with oxygen plasma. Therefore, it can be concluded that carbon dioxide supercritical fluid treatment has a tendency to improve the viability of H9c2 cells.
請再參照第8、9a、9b、9c及9d圖所示,舉例而言,本發明較佳實施例之利用超臨界流體處理多孔矽結構及其方法,相對於未處理多孔矽結構而言,其經由超臨界流體處理之多孔矽結構後,顯然其可達成提高細胞株於多孔矽結構的存活率〔即提高H9c2細胞生存力的趨勢〕。 Please refer again to Figures 8, 9a, 9b, 9c and 9d. For example, the processing of porous silicon structures and methods thereof using supercritical fluids in preferred embodiments of the present invention, compared to untreated porous silicon structures, After the porous silicon structure is treated with supercritical fluid, it is obvious that it can increase the survival rate of cell lines in the porous silicon structure (that is, the trend of increasing the viability of H9c2 cells).
前述較佳實施例僅舉例說明本發明及其技術特徵,該實施例之技術仍可適當進行各種實質等效修飾及/或替換方式予以實施;因此,本發明之權利範圍須視後附申請專利範圍所界定之範圍為準。本案著作權限制使用於中華民國專利申請用途。 The above-mentioned preferred embodiments only illustrate the present invention and its technical characteristics, and the technology of this embodiment can still be implemented in various substantially equivalent modifications and/or replacements; therefore, the scope of rights of the present invention depends on the appended patent application The scope defined by the scope shall prevail. The copyright in this case is restricted to be used for patent applications in the Republic of China.
1:矽基板 1: Silicon substrate
10:具多孔矽結構之基板 10: Substrate with porous silicon structure
11:已處理多孔矽基板 11: Processed porous silicon substrate
110:已處理多孔結構 110: processed porous structure
2:蝕刻材料 2: Etching material
3:超臨界流體 3: supercritical fluid
a:已擴大孔徑 a: enlarged aperture
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