TW201409540A - Reproduction method of sapphire substrate - Google Patents
Reproduction method of sapphire substrate Download PDFInfo
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- TW201409540A TW201409540A TW101131083A TW101131083A TW201409540A TW 201409540 A TW201409540 A TW 201409540A TW 101131083 A TW101131083 A TW 101131083A TW 101131083 A TW101131083 A TW 101131083A TW 201409540 A TW201409540 A TW 201409540A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/005—Processes
- H01L33/0062—Processes for devices with an active region comprising only III-V compounds
- H01L33/0066—Processes for devices with an active region comprising only III-V compounds with a substrate not being a III-V compound
- H01L33/007—Processes for devices with an active region comprising only III-V compounds with a substrate not being a III-V compound comprising nitride compounds
Abstract
Description
本發明係有關於一種利用全濕式製程將具有鍍層之藍寶石基板回復至藍寶石基板新片品質之藍寶石基板之再生方法。The present invention relates to a method of regenerating a sapphire substrate having a plated sapphire substrate restored to a new quality of a sapphire substrate using a full wet process.
藍寶石的組成為氧化鋁(A12O3)是由三個氧原子和兩個鋁原子以共價鍵型式結合，晶體結構為六方晶格結構，藍寶石的光學穿透帶很寬，從近紫外光(190nm)到中紅外線都有很好的透光性，並且具備高聲速、耐高溫、抗腐蝕、高硬度、熔點高及電絕緣等特點，常作為光電元件材料。隨著1993年日亞化(Nichia)開發出以氮化鎵(GaN)為材質的藍光LED，配合MOCVD(有機金屬氣相磊晶法)的磊晶技術，可製造出高亮度的藍光LED，藍寶石(Sapphire)成為製成氮化鎵磊晶發光層的主要基板材質。
然，磊晶製程並無法達到良率百分之百的程度，且藍寶石基板從長晶至切磨拋加工，也十分不易，尤其是面對日益需求的4”、6”大尺寸基板搭配表面圖案化的製程，如果因磊晶失敗而使得藍寶石基板無法再利用，對於耗能的製程實為可惜。習知在回收藍寶石基板再利用之最後一道製程會使用磨拋製程，將藍寶石基板之表面做ㄧ物理性破壞，造成圖案化之藍寶石基板無法再次使用。
習知在處理該些回收的藍寶石基板及玻璃，係需要進行下列步驟：
(a)先浸漬一第一酸液，去除金屬層；
(b)高溫(1100～1800℃)裂解氮化物；
(c)浸漬一第二酸液，去除磊晶結構氧化物；及
(d)化學機械拋光，去除表面殘餘物。
例如，中華民國專利公報公告第I366894號之「藍寶石晶圓再生方法」，其包括下列步驟：(a)提供藍寶石晶圓，此藍寶石晶圓上已形成有磊晶結構；(b)對藍寶石晶圓進行第一浸漬(Dipping)製程，以移除金屬殘留物；(c)對藍寶石晶圓進行高溫處理(High Temperature Treatment)製程以破壞及氧化磊晶結構；(d)對藍寶石晶圓進行第二浸漬製程，以移除殘餘的磊晶結構氧化物；(e)對藍寶石晶圓的第一表面進行第一拋光製程，其中藍寶石晶圓再生方法依照步驟(a)至步驟(e)的順序進行。使再生藍寶石晶圓具有與藍寶石晶圓新片相同之品質。
前案第I366894號為典型以習知製程處理藍寶石基板之再生方法，其係透過高溫裂解將去除氮化物，在長時間的再生製程中，此步驟需要進行數個小時，不僅相當耗時，且會消耗大量能源，製程之效率低落，再者，習知的藍寶石基板再生製程會依序進行兩道酸性溶液之浸漬，而酸性溶液中通常係由磷酸、硫酸、硝酸、鹽酸等強酸混合製成，浸漬過程中，蝕刻液破壞藍寶石基板表面狀態、侵蝕藍寶石基板，使藍寶石基板厚度減薄及表面粗糙度變異，若藍寶石基板表面已圖案化，亦會受到不同軸向的蝕刻率不同而被破壞。
由於現有技術尚無法完善處理此類問題，所以有加以突破、解決之必要。因此，如何提升方便性、實用性與經濟效益，此為業界應努力解決、克服之重點項目。
緣此，本發明人有鑑於習知藍寶石基板再生方法之問題缺失未臻理想之事實，本案發明人即著手研發其解決方案，希望能開發出一種更具便利性、實用性與高經濟效益之藍寶石基板之再生方法，以促進社會之發展，遂經多時之構思而有本發明之產生。The composition of sapphire is alumina (A1 2 O 3 ) which is composed of three oxygen atoms and two aluminum atoms in a covalent bond type, and the crystal structure is a hexagonal lattice structure. The optical penetration band of sapphire is very wide, from near ultraviolet Light (190nm) to medium-infrared light has good light transmission, and has the characteristics of high sound speed, high temperature resistance, corrosion resistance, high hardness, high melting point and electrical insulation, and is often used as a photovoltaic element material. With the development of a blue LED based on gallium nitride (GaN) in 1993, Nichia, together with epitaxial technology of MOCVD (organic metal vapor phase epitaxy), can produce high-brightness blue LEDs. Sapphire becomes the main substrate material for the gallium nitride epitaxial light-emitting layer.
However, the epitaxial process cannot achieve 100% yield, and the sapphire substrate is very difficult to be processed from crystal growth to cutting and polishing, especially in the face of the increasingly demanding 4", 6" large-size substrates with surface patterning. In the process, if the sapphire substrate cannot be reused due to the failure of the epitaxial crystal, it is a pity for the energy-consuming process. It is known that the last process of recycling sapphire substrates will use a grinding and polishing process to physically destroy the surface of the sapphire substrate, so that the patterned sapphire substrate cannot be reused.
It is conventional to process the recovered sapphire substrate and glass in the following steps:
(a) first impregnating a first acid solution to remove the metal layer;
(b) high temperature (1100 ~ 1800 ° C) cracking nitride;
(c) impregnating a second acid solution to remove the epitaxial oxide; and (d) chemical mechanical polishing to remove surface residues.
For example, the "Sapphire Wafer Reproduction Method" of the Republic of China Patent Publication No. I366894 includes the following steps: (a) providing a sapphire wafer on which an epitaxial structure has been formed; (b) a pair of sapphire crystals Round to perform a first Dipping process to remove metal residues; (c) to perform high temperature treatment on sapphire wafers to destroy and oxidize epitaxial structures; (d) to perform sapphire wafers a second dipping process to remove residual epitaxial oxide; (e) performing a first polishing process on the first surface of the sapphire wafer, wherein the sapphire wafer is reproduced in the order of steps (a) through (e) get on. The recycled sapphire wafer has the same quality as the new sapphire wafer.
The first method No. I366894 is a regeneration method for treating a sapphire substrate by a conventional process, which removes nitride by pyrolysis. In a long-time regeneration process, this step takes several hours, which is not only time consuming, but also It will consume a lot of energy, and the efficiency of the process is low. Moreover, the conventional sapphire substrate regeneration process will sequentially impregnate two acidic solutions, and the acidic solution is usually made of a strong acid such as phosphoric acid, sulfuric acid, nitric acid or hydrochloric acid. During the immersion process, the etchant destroys the surface state of the sapphire substrate, erodes the sapphire substrate, and reduces the thickness of the sapphire substrate and the surface roughness. If the surface of the sapphire substrate is patterned, it will be destroyed by different etch rates in different axial directions. .
Since the prior art is still unable to perfect such problems, it is necessary to break through and solve them. Therefore, how to improve convenience, practicability and economic benefits is a key project that the industry should strive to solve and overcome.
Therefore, the inventors of the present invention have developed a solution in view of the fact that the problem of the conventional sapphire substrate regeneration method is unsatisfactory, and hopes to develop a more convenient, practical and economical benefit. The method for regenerating a sapphire substrate has the purpose of promoting the development of society and the concept of the present invention.
本發明之目的在於提供一種藍寶石基板之再生方法，其係將一具有鍍層之藍寶石基板浸漬於一鹼性水溶液，以去除該藍寶石基板上之金屬氮化物層，並經一清洗製程後得到一再生之藍寶石基板，再生過程採用全濕式製程，處理量大、處理時間短、可選擇性清除鍍層，且浸漬液不與藍寶石基板反應，可保留藍寶石基板使用前狀態，降低成膜生產參數之變異性，提昇產品良率。
本發明係提供一種藍寶石基板之再生方法，其包含下列步驟：首先，提供一半導體結構，其包含一藍寶石基板及一磊晶結構，該磊晶結構設於該藍寶石基板一側；浸漬該半導體結構於一鹼性水溶液，以去除該磊晶結構之複數金屬氮化物層；取出該半導體結構，並進行一清洗製程，以去除該半導體結構之殘留浸漬液；最後，得到該藍寶石基板。An object of the present invention is to provide a method for regenerating a sapphire substrate by immersing a sapphire substrate having a plating layer in an alkaline aqueous solution to remove the metal nitride layer on the sapphire substrate, and obtaining a regeneration after a cleaning process. The sapphire substrate adopts a full wet process for regeneration. The processing volume is large, the processing time is short, and the plating layer can be selectively removed. The immersion liquid does not react with the sapphire substrate, and the sapphire substrate can be retained before use, and the variation of the film forming production parameters can be reduced. Sex, improve product yield.
The present invention provides a method for regenerating a sapphire substrate, comprising the steps of: firstly providing a semiconductor structure comprising a sapphire substrate and an epitaxial structure disposed on a side of the sapphire substrate; dipping the semiconductor structure An alkaline aqueous solution is used to remove the plurality of metal nitride layers of the epitaxial structure; the semiconductor structure is taken out, and a cleaning process is performed to remove residual immersion liquid of the semiconductor structure; finally, the sapphire substrate is obtained.
茲為使 貴審查委員對本發明之結構特徵及所達成之功效更有進一步之瞭解與認識，謹佐以較佳之實施例圖及配合詳細之說明，說明如後：
由於習知的藍寶石基板再生製程需要進行高溫裂解及化學拋光之步驟，過程中會耗費大量的能源及時間，高溫數小時耗能會破壞基板表面狀態、蝕刻液會侵蝕基板，造成基板厚度減薄及表面粗糙度變異，會提昇成膜生產參數之變異性，故本案係提出能夠改善上述缺失之藍寶石基板再生方法。
首先，請一併參閱第一A圖及第一B圖，其為本發明之第一較佳實施例之結構示意圖及實施步驟示意圖；如圖所示，本實施例之藍寶石基板再生方法，其步驟如下：
步驟S10：提供一半導體結構，其包含一藍寶石基板及一磊晶結構，該磊晶結構設於該藍寶石基板一側；
步驟S20：浸漬該半導體結構於一鹼性水溶液，以去除該磊晶結構之複數金屬氮化物層；
步驟S30：取出該半導體結構，並進行一清洗製程，以去除該半導體結構之殘留浸漬液；及
步驟S40：得到該藍寶石基板。
如第一A圖所示，該藍寶石基板10一側設置該些金屬氮化物層21，浸漬該半導體結構1於該鹼性水溶液，使該金屬氮化物層21浸漬於該鹼性水溶液，該些金屬氮化物層為一氮化鋁層、一氮化銦層、一氮化鎵層或其組合擇一者，該金屬氮化物層更包含至少一微量金屬、矽、矽氧化物或其組合擇一者，該微量金屬選自鎂、鋅或其組合擇一者，該鹼性水溶液包括一溶質及一溶劑，該溶質係選自氫氧化鉀、氫氧化鈉、氫氰酸鉀或其組合擇一者，該溶劑選自乙二醇、甘油、醇醚類或或其組合擇一者，該溶質較佳係為氫氧化鉀及氫氰酸鉀與該溶劑較佳係為乙二醇之混合，該溶質與該溶劑之濃度配比為10～50wt%，該溶質與該溶劑混合之溶液中更包含一去離子水，該去離子水之比例為0～10wt%，並於浸漬溫度90～180℃及浸漬時間介於5～30分鐘之間進行浸漬製程，在透過浸漬該鹼性水溶液及條件環境下，該些金屬氮化物層21會由該藍寶石基板10一側去除。
經過浸漬該鹼性水溶液，並去除該些金屬氮化物層21後，該半導體結構1表面會殘留部份浸漬液，接著進行清洗製程以洗去殘留之浸漬液，該清洗製程係使用一超音波裝置，並利用一去離子水洗淨該半導體結構1，該超音波裝置為浸入搖擺式、浸入靜止式、流水沖洗式之任一者，並將該超音波裝置之震盪頻率設定為40KHz以上，進行10～30分鐘之洗淨，以去除殘留之浸漬液，最後得到不具該金屬氮化物層21之該藍寶石基板10。
由於上述之步驟不經高溫裂解之步驟，故能減少藍寶石基板10再生製程之時間及能源消耗，且浸漬該半導體結構1於上述配方組成之該些溶液不易與該藍寶石基板10反應，亦即該溶液具有選擇性清除鍍層之優點，不侵蝕該藍寶石基板10，故可保留藍寶石基板10使用前之狀態，降低成膜生產參數之變異性，以提昇成品良率，且若該藍寶石基板10已圖案化，該圖案不會受到化學或物理性破壞，而得以保留。
請一併參閱第二A圖及第二B圖，其為本發明之第二較佳實施例之結構示意圖及實施步驟示意圖；如圖所示，本實施例之藍寶石基板再生方法於提供該半導體結構之步驟後，更包含以下步驟：
步驟S15：浸漬該半導體結構於一第一酸性水溶液，以去除該磊晶結構之至少一金屬層。
由於該半導體結構1之該磊晶結構20為一不良或不再利用之鍍層，該磊晶結構20不一定會具有該金屬層，而本實施例與第一實施例之差異在於該磊晶結構20包含一P型金屬層22及一N型金屬層23分別為一電極，本實施例新增之步驟則在於去除該P型金屬層22及該N型金屬層23。
如第二A圖所示，本實施例係具有該P型金屬層及設置於最頂層之金屬氮化物層21一側，該N型金屬層設置於最底層之金屬氮化物層21一側，該金屬層係選自鈦、金、鈮、鋁或其組合擇一者，該第一酸性水溶液係選自氫氟酸、硝酸、過氧化氫或其組合擇一者，該第一酸性水溶液較佳為該氫氟酸、硝酸之混合，該氫氟酸、硝酸混合液之濃度配比為0～100wt%，該氫氟酸、硝酸混合液更包含該過氧化氫及一去離子水，該過氧化氫及該去離子水之比例為0～200wt%，並於浸漬溫度60℃以下及浸漬時間介於2～30分鐘之間進行浸漬製程，在透過浸漬該第一酸性水溶液，並於該條件環境下，該P型金屬層22及該N型金屬層23會分別由最頂層及最底層之該金屬氮化物層21一側去除，之後，再依序進行浸漬該鹼性水溶液、清洗該半導體結構1等步驟。
請參閱第三圖，其為本發明之第三較佳實施例之實施步驟示意圖；如圖所示，本實施例之藍寶石基板再生方法於浸漬該半導體結構於該鹼性水溶液之步驟後，更包含以下步驟：
步驟S35：取出該半導體結構，浸漬該半導體結構於一第二酸性水溶液，以去除該半導體結構之一殘留矽或其氧化物。
由於在經過浸漬該鹼性水溶液後，該些金屬氮化物層21應已由該藍寶石基板10一側去除，然，該些金屬氮化物層21包含的矽或其氧化物可能會殘留於該藍寶石基板10一側，本實施例之步驟即在於去除該些可能殘留於該藍寶石基板10一側之矽或其氧化物，最後進行該清洗製程，以去除該半導體結構1之殘留浸漬液，而得到該藍寶石基板10。該第二酸性水溶液包括一鹽類及一溶劑，該鹽類係選自酸式氟化銨，該溶劑係選自去離子水、乙二醇、甘油、醇醚類或其組合擇一者，該溶劑較佳係選自去離子水與該乙二醇醚之混合溶液，再與該酸式氟化銨混合而成該第二酸性水溶液，該鹽類及該溶劑之濃度配比為5～20wt%，並於浸漬溫度150℃以下及浸漬時間介於10～30分鐘之間進行浸漬製程，在透過浸漬該第二酸性水溶液及條件環境下，該殘留之矽或其氧化物會由該藍寶石基板10一側去除。
請參閱第四圖，其為本發明之第四較佳實施例之實施步驟示意圖；如圖所示，本實施例之藍寶石基板再生方法於進行該清洗製程之步驟後，更包含以下步驟：
步驟S45，進行電漿乾式蝕刻於該半導體結構，以去除該半導體結構之一殘留金屬氮化物層。
在經過該清洗製程後，若該半導體結構1殘留部份該金屬氮化物層於該藍寶石基板10一側，則進行電漿乾式蝕刻於該半導體結構1，以去除該藍寶石基板10上之該殘留金屬氮化物層，利用電漿乾式蝕刻將該藍寶石基板10上之該殘留金屬氮化物層去除後，即能得到一再生之該藍寶石基板10。而步驟S15、S25或S35亦能視欲去除之鍍層類型，選擇性組合於同一製程中進行，以將該藍寶石基板10之該金屬層或殘留物確實去除。
綜上所述，本案透過將該半導體結構依序浸漬於第一酸性水溶液及鹼性水溶液後，能夠去除該藍寶石基板上之磊晶結構，得到一再生之藍寶石基板，而經由浸漬第二酸性溶液及電漿乾式蝕刻，更能確實去除殘留物，且再生過程中不藉由高溫裂解之步驟，得以縮短製程之時間，而浸漬之酸、鹼水溶液係選用不易與藍寶石基板反應之配方，故，可保留基板使用前狀態，降低成膜生產參數之變異性，提昇產品良率。
雖然本發明已以較佳實施例揭露如上，然其並非用以限定本發明，任何熟習此技藝者，在不脫離本發明之精神和範圍內，當可作些許之更動與潤飾，因此本發明之保護範圍當視後附之申請專利範圍所界定者為準。In order to give the review board members a better understanding and understanding of the structural features and the efficacies of the present invention, please refer to the preferred embodiment diagrams and the detailed descriptions as follows:
Since the conventional sapphire substrate regeneration process requires high temperature cracking and chemical polishing steps, a large amount of energy and time are consumed in the process, and high-temperature energy consumption for several hours will damage the surface state of the substrate, and the etching liquid will erode the substrate, resulting in thinning of the substrate thickness. And the variation of the surface roughness will increase the variability of the film formation production parameters. Therefore, the present invention proposes a method for regenerating the sapphire substrate which can improve the above-mentioned defects.
First, please refer to FIG. 1A and FIG. 2B, which are schematic structural diagrams and implementation steps of the first preferred embodiment of the present invention; as shown in the figure, the sapphire substrate regeneration method of the present embodiment, Proceed as follows:
Step S10: providing a semiconductor structure comprising a sapphire substrate and an epitaxial structure, the epitaxial structure being disposed on a side of the sapphire substrate;
Step S20: immersing the semiconductor structure in an alkaline aqueous solution to remove the plurality of metal nitride layers of the epitaxial structure;
Step S30: taking out the semiconductor structure and performing a cleaning process to remove residual immersion liquid of the semiconductor structure; and step S40: obtaining the sapphire substrate.
As shown in FIG. A, the metal nitride layer 21 is disposed on the side of the sapphire substrate 10, the semiconductor structure 1 is immersed in the alkaline aqueous solution, and the metal nitride layer 21 is immersed in the alkaline aqueous solution. The metal nitride layer is an aluminum nitride layer, an indium nitride layer, a gallium nitride layer or a combination thereof, and the metal nitride layer further comprises at least one trace metal, lanthanum, cerium oxide or a combination thereof. In one case, the trace metal is selected from the group consisting of magnesium, zinc or a combination thereof, and the alkaline aqueous solution comprises a solute and a solvent selected from the group consisting of potassium hydroxide, sodium hydroxide, potassium hydrogen cyanide or a combination thereof. In one case, the solvent is selected from the group consisting of ethylene glycol, glycerin, alcohol ethers or a combination thereof, and the solute is preferably a mixture of potassium hydroxide and potassium hydrogen cyanate and the solvent is preferably ethylene glycol. The concentration ratio of the solute to the solvent is 10 to 50 wt%, and the solution in which the solute is mixed with the solvent further comprises a deionized water, the ratio of the deionized water is 0 to 10 wt%, and the immersion temperature is 90 ～. The impregnation process is carried out at 180 ° C and the immersion time is between 5 and 30 minutes. Under aqueous basic conditions and the environment, the plurality of metal nitride layer 21 may be removed 10 from the side of the sapphire substrate.
After the alkaline aqueous solution is immersed and the metal nitride layer 21 is removed, a part of the immersion liquid remains on the surface of the semiconductor structure 1, and then a cleaning process is performed to wash away the residual immersion liquid. The cleaning process uses an ultrasonic wave. And cleaning the semiconductor structure 1 by using a deionized water, the ultrasonic device being immersed in a swing type, immersed in a static type, or a water flushing type, and setting the oscillation frequency of the ultrasonic device to 40 KHz or more. The immersion liquid is removed for 10 to 30 minutes to remove the remaining immersion liquid, and finally the sapphire substrate 10 having the metal nitride layer 21 is obtained.
Since the above steps are not subjected to the pyrolysis step, the time and energy consumption of the sapphire substrate 10 regeneration process can be reduced, and the solutions in which the semiconductor structure 1 is impregnated in the above composition are not easily reacted with the sapphire substrate 10, that is, The solution has the advantage of selectively removing the plating layer, does not erode the sapphire substrate 10, so the sapphire substrate 10 can be retained before use, and the variability of the film formation production parameters can be reduced to improve the yield of the finished product, and if the sapphire substrate 10 has been patterned The pattern is not subject to chemical or physical damage and is retained.
Please refer to FIG. 2A and FIG. 2B, which are schematic structural diagrams and implementation steps of a second preferred embodiment of the present invention; as shown in the figure, the sapphire substrate regeneration method of the present embodiment provides the semiconductor After the steps of the structure, the following steps are included:
Step S15: immersing the semiconductor structure in a first acidic aqueous solution to remove at least one metal layer of the epitaxial structure.
Since the epitaxial structure 20 of the semiconductor structure 1 is a poor or no-use plating layer, the epitaxial structure 20 does not necessarily have the metal layer, and the difference between the embodiment and the first embodiment lies in the epitaxial structure. 20 includes a P-type metal layer 22 and an N-type metal layer 23 respectively as an electrode. The new step in this embodiment is to remove the P-type metal layer 22 and the N-type metal layer 23.
As shown in FIG. 2A, the present embodiment has the P-type metal layer and the metal nitride layer 21 disposed on the topmost layer, and the N-type metal layer is disposed on the side of the bottommost metal nitride layer 21, The metal layer is selected from titanium, gold, rhodium, aluminum or a combination thereof, and the first acidic aqueous solution is selected from the group consisting of hydrofluoric acid, nitric acid, hydrogen peroxide or a combination thereof, and the first acidic aqueous solution is selected. Preferably, the hydrofluoric acid and the nitric acid are mixed in a concentration ratio of 0 to 100% by weight, and the hydrofluoric acid and nitric acid mixture further comprises the hydrogen peroxide and a deionized water. The ratio of hydrogen peroxide and the deionized water is 0 to 200 wt%, and the immersion temperature is 60 ° C or less and the immersion time is between 2 and 30 minutes, and the first acidic aqueous solution is immersed in the immersion process. In a conditional environment, the P-type metal layer 22 and the N-type metal layer 23 are respectively removed from the metal nitride layer 21 side of the topmost layer and the bottommost layer, and then the alkaline aqueous solution is sequentially immersed and cleaned. Semiconductor structure 1 and other steps.
Please refer to the third figure, which is a schematic diagram of the implementation steps of the third preferred embodiment of the present invention. As shown in the figure, the sapphire substrate regeneration method of the present embodiment is further immersed in the step of immersing the semiconductor structure in the alkaline aqueous solution. Contains the following steps:
Step S35: taking out the semiconductor structure, immersing the semiconductor structure in a second acidic aqueous solution to remove residual ruthenium or an oxide thereof.
Since the metal nitride layer 21 should have been removed from the side of the sapphire substrate 10 after the alkaline aqueous solution is immersed, the cerium or oxide thereof contained in the metal nitride layer 21 may remain in the sapphire. On the side of the substrate 10, the steps in this embodiment are to remove the germanium or its oxide which may remain on the side of the sapphire substrate 10, and finally perform the cleaning process to remove the residual immersion liquid of the semiconductor structure 1. The sapphire substrate 10 is. The second acidic aqueous solution comprises a salt and a solvent selected from the group consisting of acid ammonium fluoride, the solvent being selected from the group consisting of deionized water, ethylene glycol, glycerin, alcohol ethers or a combination thereof. Preferably, the solvent is selected from the group consisting of a mixed solution of deionized water and the glycol ether, and then mixed with the acid ammonium fluoride to form the second acidic aqueous solution, and the concentration ratio of the salt and the solvent is 5 to 20wt%, and the impregnation temperature is below 150 ° C and the immersion time is between 10 and 30 minutes, and the residual ruthenium or its oxide will be from the sapphire by impregnating the second acidic aqueous solution and the environment. The substrate 10 is removed on one side.
Please refer to the fourth embodiment, which is a schematic diagram of the implementation steps of the fourth preferred embodiment of the present invention. As shown in the figure, the sapphire substrate regeneration method of the embodiment further includes the following steps after performing the cleaning process:
In step S45, plasma dry etching is performed on the semiconductor structure to remove a residual metal nitride layer of the semiconductor structure.
After the cleaning process, if the semiconductor structure 1 has a portion of the metal nitride layer on the side of the sapphire substrate 10, plasma dry etching is performed on the semiconductor structure 1 to remove the residue on the sapphire substrate 10. The metal nitride layer is removed by plasma dry etching to remove the residual metal nitride layer on the sapphire substrate 10, thereby obtaining a regenerated sapphire substrate 10. Steps S15, S25 or S35 can also be selectively combined in the same process depending on the type of plating to be removed, so that the metal layer or residue of the sapphire substrate 10 is surely removed.
In summary, in the present invention, by sequentially immersing the semiconductor structure in the first acidic aqueous solution and the alkaline aqueous solution, the epitaxial structure on the sapphire substrate can be removed to obtain a regenerated sapphire substrate, and the second acidic solution is immersed. And the plasma dry etching can remove the residue more reliably, and the process of the high temperature cracking is not used in the regeneration process, and the time of the process is shortened, and the impregnated acid and alkali aqueous solution are selected from the formula which is difficult to react with the sapphire substrate, so The pre-use state of the substrate can be retained, the variability of the film formation production parameters can be reduced, and the product yield can be improved.
While the present invention has been described in its preferred embodiments, the present invention is not intended to limit the invention, and the present invention may be modified and modified without departing from the spirit and scope of the invention. The scope of protection is subject to the definition of the scope of the patent application.
1．．．半導體結構1. . . Semiconductor structure
10．．．藍寶石基板10. . . Sapphire substrate
20．．．磊晶結構20. . . Epitaxial structure
21．．．金屬氮化物層twenty one. . . Metal nitride layer
22．．．P型金屬層twenty two. . . P-type metal layer
23．．．N型金屬層twenty three. . . N-type metal layer
第一A圖為本發明之第一較佳實施例之結構示意圖；
第一B圖為本發明之第一較佳實施例之實施步驟示意圖；
第二A圖為本發明之第二較佳實施例之結構示意圖；
第二B圖為本發明之第二較佳實施例之實施步驟示意圖；
第三圖為本發明之第三較佳實施例之實施步驟示意圖；及
第四圖為本發明之第四較佳實施例之實施步驟示意圖。The first A is a schematic structural view of a first preferred embodiment of the present invention;
Figure 1B is a schematic view showing the steps of the first preferred embodiment of the present invention;
2A is a schematic structural view of a second preferred embodiment of the present invention;
2B is a schematic view showing the steps of implementing the second preferred embodiment of the present invention;
The third embodiment is a schematic diagram of the steps of the third preferred embodiment of the present invention; and the fourth diagram is a schematic diagram of the implementation steps of the fourth preferred embodiment of the present invention.
Claims (11)
提供一半導體結構，其包含一藍寶石基板及一磊晶結構，該磊晶結構設於該藍寶石基板一側；
浸漬該半導體結構於一鹼性水溶液，以去除該磊晶結構之複數金屬氮化物層；
取出該半導體結構，並進行一清洗製程，以去除該半導體結構之殘留浸漬液；及
得到該藍寶石基板。A method for regenerating a sapphire substrate, comprising:
Providing a semiconductor structure comprising a sapphire substrate and an epitaxial structure disposed on a side of the sapphire substrate;
Immersing the semiconductor structure in an alkaline aqueous solution to remove the plurality of metal nitride layers of the epitaxial structure;
The semiconductor structure is taken out and subjected to a cleaning process to remove residual immersion liquid of the semiconductor structure; and the sapphire substrate is obtained.
浸漬該半導體結構於一第一酸性水溶液，以去除該磊晶結構之至少一金屬層。The method for regenerating a sapphire substrate according to claim 1, wherein after the step of providing a semiconductor structure, the method further comprises the following steps:
The semiconductor structure is immersed in a first acidic aqueous solution to remove at least one metal layer of the epitaxial structure.
取出該半導體結構，浸漬該半導體結構於一第二酸性水溶液，以去除該半導體結構之一殘留矽或其氧化物。The method for regenerating a sapphire substrate according to claim 1, wherein after the step of immersing the semiconductor structure in an alkaline aqueous solution, the method further comprises the steps of:
The semiconductor structure is taken out and the semiconductor structure is immersed in a second acidic aqueous solution to remove residual ruthenium or an oxide thereof.
進行電漿乾式蝕刻於該半導體結構，以去除該半導體結構之一殘留金屬氮化物層。The method for regenerating a sapphire substrate according to claim 1, wherein the step of removing the semiconductor structure and performing a cleaning process to remove residual immersion liquid on the surface of the semiconductor structure further comprises the following steps:
A plasma dry etch is performed on the semiconductor structure to remove a residual metal nitride layer of the semiconductor structure.
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| CN109887878A (en) * | 2019-02-28 | 2019-06-14 | 保定中创燕园半导体科技有限公司 | A method of recycling graphical sapphire substrate |
| CN110993729B (en) * | 2019-11-20 | 2022-04-19 | 中国电子科技集团公司第十一研究所 | Indium bump resetting method for infrared detector reading circuit |
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| TWI366894B (en) * | 2008-07-22 | 2012-06-21 | Crystalwise Technology Inc | A method of reclaiming sapphire wafer |
| CN101494267B (en) * | 2008-11-24 | 2010-09-29 | 厦门市三安光电科技有限公司 | Preparation method for gallium nitride base light-emitting device based on substrate desquamation |
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