TW201205678A - Method for producing nitride compound semiconductor substrate, nitride compound semiconductor substrate and self-supporting nitride compound semiconductor substrate - Google Patents

Method for producing nitride compound semiconductor substrate, nitride compound semiconductor substrate and self-supporting nitride compound semiconductor substrate Download PDF

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TW201205678A
TW201205678A TW100107750A TW100107750A TW201205678A TW 201205678 A TW201205678 A TW 201205678A TW 100107750 A TW100107750 A TW 100107750A TW 100107750 A TW100107750 A TW 100107750A TW 201205678 A TW201205678 A TW 201205678A
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substrate
compound semiconductor
nitride
semiconductor substrate
gan
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Satoru Morioka
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Jx Nippon Mining & Amp Metals
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    • C30B29/40—AIIIBV compounds wherein A is B, Al, Ga, In or Tl and B is N, P, As, Sb or Bi
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Abstract

Disclosed is a technique for producing a high-quality GaN semiconductor substrate by stabilizing the quality of a low-temperature protective layer. A thermal etching process is carried out to make the average surface roughness of a substrate for growth 0.2 - 10 nm (first step), and epitaxial growth of a low temperature protective layer formed from a nitride compound semiconductor is carried out at 500 - 700 DEG C on the substrate for growth that has undergone this thermal etching process (second step). Thereafter, a high quality GaN semiconductor substrate is produced by carrying out epitaxial growth of a thick film layer, which is formed from a nitride compound semiconductor, at 900 - 1050 DEG C on the low-temperature protective layer (third step).

Description

201205678 六、發明說明： 【發明所屬之技術領域】 本發明係關於在成長用基板上中介著低溫保護層使氮 化物系化合物半導體層成長之氮化物系化合物半導體基板 之製造方法，氮化物系化合物半導體基板及氮化物系化合 物半導體獨立基板。 【先前技術】 從前，於基板上外延成長GaN等氮化物系化合物半導 體（以下，稱爲GaN系半導體）而成的半導體裝置（例如， 電子裝置或光裝置）係屬已知。於此半導體裝置，主要使 用由藍寶石或SiC等所構成的基板，但這些基板材料與 GaN系半導體之晶格不整合度很大，所以於其上外延成長 GaN系半導體的話，會發生應變（Strain)導致的結晶缺陷 。接著，產生於外延層的結晶缺陷，成爲半導體裝置的特 性降低的主要原因。此處，爲了解決起因於這樣的晶格不 整合之問題，被嘗試著種種成長方法。 例如，在專利文獻1，被提議了使用擬似晶格常數接 近於GaN系半導體的NdGa03基板（以下，稱爲NGO基板） 。具體而言，係被揭示了藉由氫化物氣相成長法（HVPE·. Hydride Vapor Phase Epitaxy)而在 NGO 基板上使 GaN 厚 膜成長，而製作GaN獨立基板（僅以GaN構成的基板）之 技術。在NG0基板之（011)面，NG0的a軸的長度與GaN 的[1 1-20]方向的晶格常數幾乎一致，所以可以解決前述之 201205678 起因於晶格不整合的問題。接著，藉由把GaN獨立基板作 爲半導體裝置用基板，可以謀求裝置特性的提高。 此外，GaN厚膜層的成長，一般是在1 000°C附近的成 長溫度下進行的，但是NGO基板在1 000°C附近的高溫下 暴露於原料氣體會變質，而使GaN厚膜層的結晶品質降低 。因此，被提案出在使GaN厚膜層成長之前要在600 °C附 近於NGO基板上成長被稱爲低溫保護層的GaN薄膜層， 以保護NGO基板的技術（例如專利文獻1、2)。 [先前技術文獻] [專利文獻] [專利文獻〗]日本專利特開2003-257854號公報 [專利文獻2 ]日本專利特開2 0 0 0 - 4 0 4 5號公報 【發明內容】 [發明所欲解決之課題] 然而，在從前的製造方法，隨著低溫保護層的品質之 參差不齊會有GaN厚膜層的品質受到影響的問題。例如， 在外延成長，成長層繼受下底層的結晶姓，所以低溫保護 層爲單晶的話可得單晶之GaN厚膜層，但低溫保護層爲多 晶的場合，GaN厚膜層也會變成多晶。 本發明之目的在於提供藉由使低溫保護層的品質安定 而製造高品質的GaN系半導體基板之技術。 [供解決課題之手段] -6- 201205678 申請專利範圍第1項所記載之發明，係爲了達成前述 目的而發明者，其係一種氮化物系化合物半導體基板之製 造方法’特徵爲具有：以使成長用基板之平均表面粗糙度 成爲0.2〜lOnm的方式施以熱蝕刻處理的第1步驟，於被 施以前述熱鈾刻處理的成長用基板上，在500〜700°C使氮 化物系化合物半導體構成的低溫保護層外延成長之第2步 驟’以及於前述低溫保護層上，在900〜1050 °C使氮化物 系化合物半導體所構成的厚膜層外延成長的第3步驟。 申請專利範圍第2項之發明，係如申請專利範圍第1 項之氮化物系化合物半導體基板之製造方法，特徵爲在前 述第1步驟，使前述成長用基板在900〜105CTC保持5分 鐘以內。 申請專利範圍第3項之發明，係如申請專利範圍第1 或2項之氮化物系化合物半導體基板之製造方法，特徵爲 前述成長用基板係以稀土類鈣鈦礦（perovskite)構成的。 申請專利範圍第4項之發明，係如申請專利範圍第3 項之氮化物系化合物半導體基板之製造方法，特徵爲前述 成長用基板係以NdGa03構成的。 申請專利範圍第5項之發明，係由申請專利範圍第1 至4項之任一項之製造方法所製造的氮化物系化合物半導 體基板。 申請專利範圍第6項之發明，係由申請專利範圍第5 項之氮化物系化合物半導體基板剝離前述氮化物系化合物 半導體層，切片、硏磨加工而得的氮化物系化合物半導體 201205678 獨立基板。 以下，說明直到完成本發明之過程。[Technical Field] The present invention relates to a method for producing a nitride-based compound semiconductor substrate in which a nitride-based compound semiconductor layer is grown by interposing a low-temperature protective layer on a growth substrate, and a nitride-based compound. A semiconductor substrate and a nitride-based compound semiconductor independent substrate. [Prior Art] Conventionally, a semiconductor device (for example, an electronic device or an optical device) in which a nitride-based compound semiconductor such as GaN (hereinafter referred to as a GaN-based semiconductor) is epitaxially grown on a substrate is known. In this semiconductor device, a substrate made of sapphire or SiC is mainly used. However, these substrate materials have a large degree of lattice incompatibility with a GaN-based semiconductor. Therefore, when a GaN-based semiconductor is epitaxially grown, strain occurs (Strain). ) caused by crystal defects. Then, the crystal defects generated in the epitaxial layer are a cause of a decrease in the characteristics of the semiconductor device. Here, in order to solve the problem caused by such lattice unconformity, various growth methods have been tried. For example, in Patent Document 1, it is proposed to use a NdGaO substrate (hereinafter referred to as an NGO substrate) having a pseudo lattice constant close to a GaN-based semiconductor. Specifically, it has been disclosed that a GaN thick film is grown on an NGO substrate by a hydride vapor phase growth method (HVPE·.Hydride Vapor Phase Epitaxy) to form a GaN independent substrate (a substrate made only of GaN). technology. On the (011) plane of the NG0 substrate, the length of the a-axis of NG0 is almost identical to the lattice constant of the [1 1-20] direction of GaN, so that the aforementioned problem of lattice unconformity due to 201205678 can be solved. Then, by using a GaN independent substrate as a substrate for a semiconductor device, it is possible to improve the device characteristics. In addition, the growth of the GaN thick film layer is generally performed at a growth temperature of around 1 000 ° C, but the exposure of the NGO substrate to the raw material gas at a high temperature around 1 000 ° C deteriorates, and the GaN thick film layer is The crystal quality is lowered. Therefore, a technique of protecting a GaN substrate by forming a GaN thin film layer called a low temperature protective layer on the NGO substrate at 600 °C before the growth of the GaN thick film layer has been proposed (for example, Patent Documents 1 and 2). [PRIOR ART DOCUMENT] [Patent Document] [Patent Document] Japanese Patent Laid-Open Publication No. 2003-257854 [Patent Document 2] Japanese Patent Laid-Open Publication No. 2000-2004 Problem to be Solved] However, in the conventional manufacturing method, the quality of the GaN thick film layer is affected as the quality of the low temperature protective layer is uneven. For example, in the epitaxial growth, the growth layer is subjected to the crystallographic surname of the lower layer. Therefore, if the low temperature protective layer is a single crystal, a single crystal GaN thick film layer can be obtained. However, when the low temperature protective layer is polycrystalline, the GaN thick film layer is also Become polycrystalline. An object of the present invention is to provide a technique for producing a high-quality GaN-based semiconductor substrate by setting the quality of the low-temperature protective layer. [Means for Solving the Problems] -6-201205678 The invention described in the first aspect of the invention is a method for producing a nitride-based compound semiconductor substrate, which is characterized in that: The first step of the thermal etching treatment is performed so that the average surface roughness of the growth substrate is 0.2 to 1 nm, and the nitride compound is applied at 500 to 700 ° C on the growth substrate subjected to the thermal uranium engraving treatment. The second step of epitaxial growth of the low temperature protective layer of the semiconductor structure and the third step of epitaxially growing the thick film layer of the nitride-based compound semiconductor at 900 to 1050 ° C on the low temperature protective layer. The invention of claim 2 is the method for producing a nitride-based compound semiconductor substrate according to the first aspect of the invention, characterized in that in the first step, the growth substrate is held at 900 to 105 CTC for 5 minutes or less. The invention of claim 3 is the method for producing a nitride-based compound semiconductor substrate according to claim 1 or 2, wherein the growth substrate is made of a rare earth perovskite. The invention of claim 4 is the method for producing a nitride-based compound semiconductor substrate according to claim 3, wherein the growth substrate is made of NdGa03. The invention of claim 5 is a nitride-based compound semiconductor substrate produced by the production method according to any one of claims 1 to 4. The invention of claim 6 is a nitride-based compound semiconductor 201205678 independent substrate obtained by exfoliating the nitride-based compound semiconductor layer from the nitride-based compound semiconductor substrate of the fifth application of the patent application, and slicing and honing. Hereinafter, the process up to the completion of the present invention will be described.

本案發明人等，首先，升溫至特定的退火溫度（80(TC ' 9GG°C、l〇〇〇°C)後，對NGO基板施以保持特定時間的退 火處理，藉由NGO基板之X線半高寬來調查加熱所導致 的NGO基板的特性變化。又，退火溫度爲8 00°C、900°C 的場合之保持時間爲5分鐘，1 000 °C的場合之保持時間爲 5〜15分鐘。 於圖1顯示退火溫度與N GO基板之X線半高寬的關 係。又，退火溫度0°C的X線半高寬，是退火處理前之 NGO基板的X線半高寬。如圖1所示，相對於退火處理 前之NGO基板的X線半高寬爲18.36秒，退火處理後之 NGO基板的X線半高寬爲16〜23秒。即使退火處理前的 基板，數値也會有此程度之參差不齊，所以可說是退火不 會導致NGO基板的X線半高寬改變。 其次，針對前述之施以退火處理的NGO基板，調查 退火溫度與NGO基板的表面粗糙度Ra之關係。具體而言 ，藉由原子間力顯微鏡（AFM: Atomic Force Microscope)， 於5μιηχ5μΓη之測定範圍，測定NGO基板表面之面內的中 心1點以及位於通過中心點的直交軸上的周緣部的4點合 計5點之表面粗糙度，算出5個測定點之表面粗糙度的平 均値（平均表面粗糙度）。 於圖2顯示退火溫度與NGO基板之平均表面粗糙度 的關係。又，退火溫度〇°C的表面粗糙度，是退火處理前 -8- 201205678 之NGO基板的表面粗糖度。如圖2所示，退火處理前的 NGO基板是非常平坦的表面，平均表面粗糙度爲〇.151nm 。相對於此，施以800°C x5分的退火處理的NGO基板平 均表面粗糙度成爲0.195 nm，伴隨著退火溫度的上升表面 粗糙度變大。此外，在施以l〇〇(TC之退火處理的NGO基 板，伴隨著保持時間變長，表面粗糙度變大。 進而，在施以前述退火處理的NGO基板上，使GaN 低溫保護層成長。此時，以使HC1的供給分壓爲2.19xl(T2atm ，使NH3的供給分壓爲6.58 χ1 (Γ2atm的方式供給原料氣體 。此外，GaN低溫保護層之成長溫度爲600°C » 圖3顯示NGO基板之平均表面粗糙度與GaN低溫保 護層的X線半高寬的關係。如圖3所示，NGO基板之平 均表面粗糙度爲0.2〜lOnm的範圍的場合，可得X線半高 寬爲1 000秒以下的單晶所構成的GaN低溫保護層。另一 方面，NGO基板之平均表面粗糙度在0.2nm以下及l〇nm 以上，會成爲半高寬爲3000秒以上的多晶所構成的GaN 低溫保護層。 接著，根據相關之發現反覆進行GaN低溫保護層的成 膜實驗的結果，確認了藉由使NGO基板的平均表面粗糙 度收在0.2〜10nm的範圍，可以安定地獲得優質的GaN低 溫保護層，從而完成本發明。 從前，應該是由於GaN成長之升溫程序導致加熱時間 過長而使NGO基板表面太過粗糙，因而使得GaN低溫保 護層之品質參差不齊。 -9 - 201205678 本案發明人等，對於NGO基板的表面粗糙度與GaN 結晶的結晶性的關係還不是很清楚，但是仍推想NGO基 板表面之缺陷位置（kink site)的數目應該會影響GaN結晶 的結晶性。亦即，可能當NGO基板的表面相當粗糙而缺 陷位置（kink site)太多時，於GaN成長初期會大量引發核 發生而導致多晶化，另一方面，NGO基板的表面粗糙度很 小時缺陷位置（kink site)太少，所以不容易引起核發生， 因而析出多晶。 [發明之效果] 根據本發明，藉由熱蝕刻處理以NGO基板的平均表 面粗糙度成爲所要的範圍的方式進行控制，可以於NGO 基板上使優質的低溫保護層安定地成長，所以可以於此上 再現性佳地成長高品質的GaN厚膜層，可以製造高品質的 GaN系半導體基板。 【實施方式】 以下，針對本發明之實施形態進行詳細說明。 在本實施形態，說明利用HVPE法，於稀土類鈣鈦礦 (perovskite)所構成的NGO基板上，外延成長GaN系半導 體之GaN，製造GaN基板的方法。在HVPE法，使由III 族金屬之Ga與HC1產生的氯化物氣體（GaCl)與NH3反應 ，於基板上使GaN層外延成長。 在本實施形態，以使GaN低溫保護層之成長之前的 -10- 201205678 NGO基板的平均表面粗糖度成爲0.2〜l〇nm的方式施以熱 蝕刻處理。這是因爲GaN低溫保護層之成長之前的NGO 基板之平均表面粗糙度在〇·2ηιη以下或者l〇nm以上，會 無法安定地得到優質的GaN低溫保護層。 一般，使用於GaN成長的NGO基板的平均表面粗糙 度爲0.10〜0.17nm程度，在此場合，藉由在900〜1050 °c 之熱蝕刻溫度，保持5分鐘以內，可以控制使NGO基板 之表面粗糙度收在所要的範圍。熱蝕刻處理之保持時間超 過5分鐘的話，NGO基板的表面有太過粗糙的傾向，所以 保持時間以在5分鐘以內爲較佳。 [實施例] 在實施例，將平均表面粗糙度爲0.15 nm的NGO基板 配置於基板保持具，升溫至90(TC後，進行保持5分鐘之 熱蝕刻。此熱鈾刻後之NGO基板的平均表面粗糙度爲 0.52nm。接著，降溫至600°C後，往此NGO基板上，以 N2爲承載氣體供給由被配置在裝置內的鎵金屬與HC1氣 體所產生的GaCl，與NH3氣體時，以HC1的供給分壓成 爲2.19x l(T2atm、NH3的供給分壓成爲6.58xl0_2atm的方 式供給原料氣體，使成長50nm之GaN低溫保護層。 所得到的GaN低溫保護層，X線半高寬爲3 50秒爲結 晶性優異，C軸配向之優質的單晶。 接著，升溫至1 000°C後，爲了使溫度安定保持了 I5 分鐘。接著，於GaN低溫保護層上，以使HC1的供給分 -11 - 201205678 壓爲l.〇6M(T2atm，使NH3的供給分壓爲5.0〇xl(T2atm的 方式供給原料氣體，形成3000pm的GaN厚膜層。所得到 的GaN厚膜層爲優質的單晶，X線半高寬爲250秒。 [比較例1] 在比較例1，將平均表面粗糙度爲0.1 5nm的NGO基 板配置於基板保持具，升溫至8 00 °C後，進行保持5分鐘 之熱蝕刻。此熱蝕刻後之NGO基板的平均表面粗糙度爲 0.1 9nm。接著，與實施例同樣使GaN低溫保護層成長。所 得到的GaN低溫保護層，X線半高寬爲3 500秒，爲配向 性很差的多晶。 接著，於此GaN低溫保護層之上，與實施例同樣進行 而使GaN厚膜層成長。所得到的GaN厚膜層爲多晶，X 線半高寬爲3 3 0 0秒。 [比較例2] 在比較例2，將平均表面粗糙度爲〇.15nm的NGO基 板配置於基板保持具，升溫至l〇〇〇°C後，進行保持15分 鐘之熱蝕刻。此熱蝕刻後之NGO基板的平均表面粗糙度 爲13nm。接著，與實施例同樣使GaN低溫保護層成長。 所得到的G aN低溫保護層，X線半高寬爲3 1 00秒，爲配 向性很差的多晶。The inventors of the present invention first heated the temperature to a specific annealing temperature (80 (TC ' 9 GG ° C, 10 ° C), and then applied an anneal treatment to the NGO substrate for a specific period of time, by X-ray of the NGO substrate. The full width at half maximum is used to investigate the change in the characteristics of the NGO substrate caused by heating. In addition, the holding time is 5 minutes for annealing temperatures of 800 ° C and 900 ° C, and 5 to 15 for 1 000 ° C. Min. The relationship between the annealing temperature and the X-ray half-width of the N GO substrate is shown in Fig. 1. Further, the X-ray half-height width of the annealing temperature of 0 °C is the X-ray half-height width of the NGO substrate before the annealing treatment. As shown in Fig. 1, the X-ray half-height width of the NGO substrate before the annealing treatment is 18.36 seconds, and the X-ray half-height width of the NGO substrate after the annealing treatment is 16 to 23 seconds. Even if the substrate before annealing is processed, the number is 値There is also a degree of unevenness, so it can be said that the annealing does not cause the X-ray half-width variation of the NGO substrate. Secondly, the annealing temperature and the surface roughness of the NGO substrate are investigated for the anneal-treated NGO substrate. Degree Ra. Specifically, by atomic force microscope (AFM: Atomic Force M Icoscope), in the measurement range of 5 μm χ 5 μΓη, the surface roughness of the center point of the surface of the NGO substrate and the four points of the four points of the peripheral portion on the orthogonal axis passing through the center point were measured, and the surface of the five measurement points was calculated. The average roughness of the roughness (average surface roughness). The relationship between the annealing temperature and the average surface roughness of the NGO substrate is shown in Fig. 2. Again, the surface roughness of the annealing temperature 〇 °C is -8-201205678 before the annealing treatment. The surface roughness of the NGO substrate. As shown in Fig. 2, the NGO substrate before the annealing treatment is a very flat surface with an average surface roughness of 151.151 nm. In contrast, an NGO treated with 800 ° C x 5 minutes of annealing is applied. The average surface roughness of the substrate is 0.195 nm, and the surface roughness increases as the annealing temperature increases. Further, the surface roughness becomes larger as the NGO substrate subjected to the annealing treatment of TC becomes longer as the holding time becomes longer. Further, on the NGO substrate subjected to the annealing treatment, the GaN low temperature protective layer is grown. At this time, the partial pressure of the supply of HC1 is 2.19 x 1 (T2 atm, and the partial pressure of NH 3 is 6.58 χ1). (The raw material gas is supplied in a manner of 2 atm. In addition, the growth temperature of the GaN low temperature protective layer is 600 ° C.) Fig. 3 shows the relationship between the average surface roughness of the NGO substrate and the X-ray half-width of the GaN low-temperature protective layer. When the average surface roughness of the NGO substrate is in the range of 0.2 to 1 nm, a GaN low-temperature protective layer composed of a single crystal having an X-ray half-height width of 1 000 seconds or less can be obtained. On the other hand, the average surface of the NGO substrate is obtained. When the roughness is 0.2 nm or less and 10 nm or more, a GaN low-temperature protective layer composed of polycrystals having a full width at half maximum of 3000 seconds or more is obtained. Then, based on the results of the film formation test of the GaN low-temperature protective layer, it was confirmed that the high-quality GaN low-temperature protective layer can be stably obtained by setting the average surface roughness of the NGO substrate to a range of 0.2 to 10 nm. Thus, the present invention has been completed. In the past, it was supposed that the heating time was too long due to the heating process of GaN growth, and the surface of the NGO substrate was too rough, which made the quality of the GaN low temperature protective layer uneven. -9 - 201205678 The inventors of the present invention are not clear about the relationship between the surface roughness of NGO substrates and the crystallinity of GaN crystals, but it is still assumed that the number of kink sites on the surface of NGO substrates should affect the crystallization of GaN. Crystallinity. That is, when the surface of the NGO substrate is rather rough and there are too many kink sites, a large amount of nucleation occurs in the initial stage of GaN growth, resulting in polycrystallization. On the other hand, the surface roughness of the NGO substrate is small. The kink site is too small, so it is not easy to cause nucleation, and thus polycrystals are precipitated. [Effects of the Invention] According to the present invention, by controlling the average surface roughness of the NGO substrate to a desired range by thermal etching, a high-quality low-temperature protective layer can be stably grown on the NGO substrate. It is possible to produce a high-quality GaN-based semiconductor substrate by highly growing a high-quality GaN thick film layer. [Embodiment] Hereinafter, embodiments of the present invention will be described in detail. In the present embodiment, a method of producing a GaN substrate by epitaxially growing GaN of a GaN-based semiconductor on an NGO substrate made of a rare earth perovskite by the HVPE method will be described. In the HVPE method, a chloride gas (GaCl) generated from Ga of a group III metal and HCl is reacted with NH3 to epitaxially grow a GaN layer on a substrate. In the present embodiment, the etch-etching treatment is performed so that the average surface roughness of the -10-201205678 NGO substrate before the growth of the GaN low-temperature protective layer is 0.2 to 1 〇 nm. This is because the average surface roughness of the NGO substrate before the growth of the GaN low-temperature protective layer is below 〇·2ηηη or above 10 nm, and a high-quality GaN low-temperature protective layer cannot be stably obtained. Generally, the average surface roughness of the NGO substrate grown for GaN is about 0.10 to 0.17 nm. In this case, the surface of the NGO substrate can be controlled by holding the thermal etching temperature at 900 to 1050 ° C for 5 minutes or less. The roughness is within the desired range. When the holding time of the thermal etching treatment exceeds 5 minutes, the surface of the NGO substrate tends to be too rough, so the holding time is preferably within 5 minutes. [Examples] In the examples, an NGO substrate having an average surface roughness of 0.15 nm was placed on a substrate holder, and the temperature was raised to 90 (TC, and then heat-etched for 5 minutes. The average NGO substrate after the hot uranium engraving) The surface roughness is 0.52 nm. Then, after cooling to 600 ° C, when GaCl and NH 3 gas generated by gallium metal and HCl gas disposed in the device are supplied to the NGO substrate with N 2 as a carrier gas, The raw material gas was supplied so that the supply partial pressure of HC1 was 2.19×1 (the supply partial pressure of T2atm and NH3 was 6.58×10 −2 atm, and the GaN low-temperature protective layer was grown to 50 nm. The obtained GaN low-temperature protective layer had an X-ray half-height width of 3 50 seconds is a high-quality single crystal with excellent crystallinity and C-axis alignment. Then, after raising the temperature to 1 000 ° C, the temperature is maintained for 1 to 5 minutes. Next, on the GaN low-temperature protective layer, the supply of HC1 is divided. -11 - 201205678 The pressure is l.〇6M (T2atm, the supply of NH3 is divided into 5.0〇xl (the feed gas is supplied in a T2atm manner to form a GaN thick film layer of 3000 pm. The obtained GaN thick film layer is a high quality single sheet). Crystal, X-ray half-height width is 250 seconds. [Comparative Example 1] In Comparative Example 1, an NGO substrate having an average surface roughness of 0.15 nm was placed on a substrate holder, and after heating to 800 ° C, thermal etching was performed for 5 minutes. The average surface roughness of the NGO substrate after the thermal etching was 0.1 9 nm. Then, the GaN low-temperature protective layer was grown in the same manner as in the example. The obtained GaN low-temperature protective layer had a X-ray half-height width of 3 500 seconds, which was a poorly oriented polycrystal. The GaN thick film layer was grown on the layer in the same manner as in the example. The obtained GaN thick film layer was polycrystalline, and the X-ray half-height width was 3,300 seconds. [Comparative Example 2] In Comparative Example 2, An NGO substrate having an average surface roughness of 〇.15 nm was placed on a substrate holder, and the temperature was raised to 10 ° C, and then thermally etched for 15 minutes. The average surface roughness of the NGO substrate after the thermal etching was 13 nm. Then, the GaN low temperature protective layer was grown in the same manner as in the examples. The obtained GaN low temperature protective layer had a X-ray half-height width of 3 1.00 sec and was a poorly oriented polycrystal.

接著，於此GaN低溫保護層之上，與實施例同樣進行 而使GaN厚膜層成長。所得到的GaN厚膜層爲多晶，X -12- 201205678 線半高寬爲3000秒。 如此，藉由使GaN低溫保護層之成長之前的NGO基 板之平均表面粗糙度控制在〇.2nm〜10nm，可以於NGO 基板上安定地成長優質的GaN低溫保護層。此外，可以在 此GaN低溫保護層上使高品質的GaN厚膜層再現性佳地 成長，可以製造高品質的GaN系半導體基板。 進而，藉由把由此GaN基板剝離GaN厚膜層，切片 、硏磨加工而得的GaN獨立基板用於半導體裝置的製造， 可以謀求裝置性能的提高。 以上根據實施形態具體說明根據本案發明人所進行的 發明，但本發明並不以上述實施形態爲限，在不逸脫其要 旨的範圍內當然可進行變更。 在實施形態說明了在NGO基板上成長氮化物系化合 物半導體之GaN的場合，但在NGO基板上成長GaN以外 的氮化物系化合物半導體層的場合也可以適用本發明。此 處，所謂氮化物系化合物半導體，係以InxGayAl|.x.yN (O^x + y^ 1 > 1 - OSySl)表示之化合物半導體，例 如有 GaN、InGaN、AlGaN，InGaAIN 等。 此外，在實施形態針對利用HVPE法的場合進行了說 明’但利用有機金屬氣相成長法（MOCVD: Metal Organic Chemical Vapor Deposition)或分子線外延法（MBE: Molecular Beam Epitaxy)來外延成長氮化物系化合物半導 體層的場合也可以適用本發明》 此外，作爲成長用基板在使用NGO基板以外的稀土 -13- 201205678 類鈣鈦礦（perovskite)基板（例如NdA103 ’ Ndln03等）的場 合也可以適用。 本次揭示之實施形態，所有各點僅爲例示不應該視爲 限制條件。本發明之範圍不以前述說明爲限而係如申請專 利範圍所示，進而還意圖包括與申請專利範圍均等之範圍 內的所有變更。 【圖式簡單說明】 圖1係顯示退火溫度與NGO基板之X線半高寬的關 係之圖。 圖2係顯示退火溫度與NGO基板之平均表面粗糙度 的關係之圖。 圖3係顯示NGO基板之平均粗糙度與GaN厚膜層的 X線半高寬的關係之圖。 -14-Next, on the GaN low-temperature protective layer, a GaN thick film layer was grown in the same manner as in the example. The obtained GaN thick film layer is polycrystalline, and the X -12-201205678 line has a full width at half maximum of 3000 seconds. Thus, by controlling the average surface roughness of the NGO substrate before the growth of the GaN low-temperature protective layer to 〇. 2 nm to 10 nm, it is possible to stably grow a high-quality GaN low-temperature protective layer on the NGO substrate. Further, a high-quality GaN thick film layer can be reproducibly grown on the GaN low-temperature protective layer, and a high-quality GaN-based semiconductor substrate can be manufactured. Further, by peeling off the GaN thick film layer from the GaN substrate, the GaN independent substrate obtained by slicing and honing is used for the production of the semiconductor device, and the device performance can be improved. The invention made by the inventors of the present invention is specifically described above based on the embodiments, but the present invention is not limited to the above-described embodiments, and may be modified within the scope of the invention. In the case where GaN of a nitride-based compound semiconductor is grown on an NGO substrate, the present invention is also applicable to a case where a nitride-based compound semiconductor layer other than GaN is grown on an NGO substrate. Here, the nitride-based compound semiconductor is a compound semiconductor represented by InxGayAl|.x.yN (O^x + y^ 1 > 1 - OSySl), and examples thereof include GaN, InGaN, AlGaN, InGaAIN, and the like. Further, in the embodiment, the HVPE method has been described. However, the nitride system is epitaxially grown by MOCVD (Metal Organic Chemical Vapor Deposition) or Molecular Beam Epitaxy (MBE). In the case of the compound semiconductor layer, the present invention can also be applied. When the substrate for growth is used, a rare earth-13-201205678 perovskite substrate (for example, NdA103 'Ndln03 or the like) other than the NGO substrate can be used. In the embodiments disclosed herein, all points are merely exemplary and should not be considered as limiting. The scope of the present invention is not intended to be limited by the scope of the appended claims. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a graph showing the relationship between the annealing temperature and the X-ray half-width of an NGO substrate. Fig. 2 is a graph showing the relationship between the annealing temperature and the average surface roughness of the NGO substrate. Fig. 3 is a graph showing the relationship between the average roughness of the NGO substrate and the X-ray half-width of the GaN thick film layer. -14-

Claims (1)

201205678 七、申請專利範圍： 1.一種氮化物系化合物半導體基板之製造方法，其特 徵爲具有： 以使成長用基板之平均表面粗糙度成爲0.2〜10nm而 施以熱蝕刻處理的第1步驟， 於被施以前述熱蝕刻處理的成長用基板上，在500〜 7〇〇 °C使氮化物系化合物半導體構成的低溫保護層爲外延 成長之第2步驟，以及 於前述低溫保護層上，在900〜1050 °C使氮化物系化 合物半導體所構成的厚膜層爲外延成長的第3步驟。 2 ·如申請專利範圍第1項之氮化物系化合物半導體基 板之製造方法’其中在前述第1歩驟，使前述成長用基板 在900〜1 050°C保持5分鐘以內。 3.如申請專利範圍第丨或2項之氮化物系化合物半導 體基板之製造方法，其中前述成長用基板係以稀土類鈣鈦 礦（perovskite)構成的。 4·如申請專利範圍第3項之氮化物系化合物半導體基 板之製造方法，其中前述成長用基板係以NdGa03構成的 〇 5. —種氮化物系化合物半導體基板，其特徵係由申請 專利範圍第1至4項之任一項之製造方法所製造的。 6. —種氮化物系化合物半導體獨立基板，其特徵係由 如申請專利範圍第5項之氮化物系化合物半導體基板剝離 前述氮化物系化合物半導體層，切片、硏磨加工而得的。 -15-201205678 VII. Patent application scope: 1. A method for producing a nitride-based compound semiconductor substrate, comprising: a first step of subjecting a growth substrate to an average surface roughness of 0.2 to 10 nm and performing a thermal etching treatment; On the growth substrate subjected to the thermal etching treatment, a low temperature protective layer made of a nitride-based compound semiconductor at 500 to 7 ° C is a second step of epitaxial growth, and on the low temperature protective layer The thick film layer composed of the nitride-based compound semiconductor is a third step of epitaxial growth at 900 to 1050 °C. 2. The method for producing a nitride-based compound semiconductor substrate according to the first aspect of the invention, wherein in the first step, the growth substrate is held at 900 to 1 050 ° C for 5 minutes or less. 3. The method for producing a nitride-based compound semiconductor substrate according to claim 2 or 2, wherein the growth substrate is made of a rare earth perovskite. 4. The method for producing a nitride-based compound semiconductor substrate according to the third aspect of the invention, wherein the substrate for growth is a ruthenium-based nitride-based compound semiconductor substrate comprising NdGa03, which is characterized by a patent application scope. Manufactured by the manufacturing method of any one of items 1 to 4. A nitride-based compound semiconductor-independent substrate obtained by stripping and honing the nitride-based compound semiconductor layer of the nitride-based compound semiconductor substrate of the fifth aspect of the invention. -15-
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