--- ^ A 〆 五、發明說明（1) 本發明是有關於三族金屬IL化物元件之製造方法，特 別是有關改善三族金屬氮化物磊晶層與氡化鋁基板晶格不 匹配問題的製造方法。 三族金屬氮化物的磊晶成長研究由來已久，其優點在 於可以有各種不同比例的三元及四元化合物，可以調整能 隙寬度、晶格常數及折射率等’故在光電元件及高速元件 的應用有相當的潛力’在短波長發光二極體及雷射二極體 都有不錯的表現，並有達到量產程度的元件開發出來。 但其缺點在於基板價格昂貴，造價偏高，且因基板為 氧化鋁（sapphire) ’和成長的磊晶層有晶格不匹配的問 題，而在1997年底，日亞化學公司推出壽命長達一萬小時 的藍光雷射二極體’其秘訣便在於降低磊晶層與基板晶格 不匹配的問題，故基板的特性將嚴重影響磊晶膜的品質。 依據曰亞化學公司提出之方法，其緩衝層只有〇 〇(π 〜0. 5 " m，由於未能完全有效隔絕磊晶層與基板間因晶格 常數不同’所造成之缺陷延伸’故而晶格不匹配的問題仍 然存在。 有鑑於此，本發明之目的為提出一種新穎的製造方 法，主要係提供一厚度大於的緩衝層，以在上述緩 衝層上成長一層三族金屬氮化物的厚磊晶層（第一磊晶 層），藉此，來降低蠢晶層與基板間因晶格常數不同，而 造成的缺陷延伸問題。如此一來，在上述厚磊晶層上成長 ，族金^氮化物磊晶層（第二磊晶層）或元件結構時’由於 疋同質aa故無晶格匹配的問題，而上述問題即可獲得--- ^ A 〆V. Description of the invention (1) The present invention relates to a method for manufacturing a Group III metal IL compound element, and in particular, it relates to improving the lattice mismatch between the Group III metal nitride epitaxial layer and the aluminum halide substrate. Manufacturing method. The epitaxial growth of three-group metal nitrides has been studied for a long time. Its advantage is that it can have ternary and quaternary compounds in various ratios. It can adjust the energy gap width, lattice constant, and refractive index. The application of components has considerable potential. Both short-wavelength light-emitting diodes and laser diodes have good performance, and components that have reached the mass production level have been developed. However, its disadvantages are that the substrate is expensive and the cost is high. Because the substrate is sapphire and the growing epitaxial layer has a lattice mismatch problem, at the end of 1997, Nichia Chemical Co. The secret of 10,000 hours of blue laser diode is to reduce the mismatch between the epitaxial layer and the substrate lattice, so the characteristics of the substrate will seriously affect the quality of the epitaxial film. According to the method proposed by Yueya Chemical Company, its buffer layer is only 〇〇 (π ~ 0.5 " m, because the failure to completely isolate the epitaxial layer and the substrate due to the difference in lattice constants caused by the lattice extension " The problem of lattice mismatch still exists. In view of this, the object of the present invention is to propose a novel manufacturing method, which is mainly to provide a buffer layer with a thickness greater than that to grow a layer of Group III metal nitride on the buffer layer. The epitaxial layer (first epitaxial layer) is used to reduce the defect extension problem caused by the difference in lattice constant between the stupid layer and the substrate. As a result, the thick epitaxial layer grows on the thick epitaxial layer. ^ In the case of nitride epitaxial layer (second epitaxial layer) or element structure, there is no problem of lattice matching due to homogeneous aa, and the above problem can be obtained.
五、發明說明（2) 改善。 為達成上述目的，本發明提出之三族金屬氮化物厚義 晶層的製造方法，包括： 成長三族金屬氮化物緩衝層於一氧化鋁基板上；上述 緩衝層薄膜’例如由HVPE法、MOCVD法、或MBE法製作而 得’其厚度大於0.5jwm。 使用HVPE法、或MOCVD法’在上述三族金屬氮化物緩 衝層上成長一層三族金屬氮化物厚磊晶層（第一磊晶層）， 例如為1 0 // in以上。 使用MOCVD法、MBE法、或HVPE法，在上述三族金屬氮 化物蠢晶層薄膜上成長三族金屬氮化物高品質遙晶層（第 二蟲晶層）或元件結構。 圖式之簡單說明： 為讓本發明之上述目的、特徵、和優點能更明顯易 懂’下文特舉較佳實施例’並配合所附圖式’做詳細說明 如下： ----- 第1圖顯示第二磊晶層/元件結構、第一磊晶層、與基 板之結構剖面示意圖； 第2圖顯示三族金屬氮化物厚磊晶層之光激光頻譜 圖；以及 第3圖顯示三族金屬氮化物厚磊晶層之X光繞射光譜 圖。 符號說明： 1 〇 ~氧化鋁基板；V. Description of the invention (2) Improvement. In order to achieve the above object, the method for manufacturing a group III metal nitride thick sense crystal layer provided by the present invention includes: growing a group III metal nitride buffer layer on an alumina substrate; and the buffer layer film is, for example, a HVPE method or a MOCVD method. , Or MBE method to obtain 'thickness greater than 0.5jwm. A HVPE method or a MOCVD method is used to grow a thick Group III metal nitride epitaxial layer (first epitaxial layer) on the above Group III metal nitride buffer layer, for example, 1 0 // in or more. A MOCVD method, a MBE method, or an HVPE method is used to grow a group III metal nitride high-quality telemorphic layer (second parasite layer) or a device structure on the above-mentioned group III metal nitride layer film. Brief description of the drawings: In order to make the above-mentioned objects, features, and advantages of the present invention more comprehensible, the following exemplifies preferred embodiments and the accompanying drawings, as follows: Figure 1 shows a schematic cross-sectional view of the structure of the second epitaxial layer / element structure, the first epitaxial layer, and the substrate; Figure 2 shows the optical laser spectrum of a thick epitaxial layer of a group III metal nitride; and Figure 3 shows three X-ray diffraction spectrum of a thick epitaxial layer of a group metal nitride. Explanation of symbols: 1 0 ~ alumina substrate;
五、發明說明（3) 11〜（氮化鎵）緩衝層； 1 2〜第一磊晶層（氮化鎵厚磊晶層）； 1 3〜第二磊晶層/元件結構。 實施例： 本發明主要目的在提供一種改善三族金屬氮化物磊晶 層與氧化铭基板晶格不匹配問題的三族金屬氮化物之製造 方法。 第1圖顯示本發明實施例中，第二磊晶層/元件結構、 第—蠢晶層、與基板之結構剖面示意圖。 參照第1圖’依據本發明的三族金屬氮化物元件之製 造方法，包括如下所述之步驟。 首先’成長緩衝層11(或緩衝薄膜）於氧化鋁基板1〇 上；其中’上述緩衝層11係為厚度大於05/ζπ1之三族金屬 氮化物。 上述緩衝層11 ’係使用有機金屬化學氣相沈積法 (MOCVD) ’分子束最晶法（jjbe)、或齒化物化學氣相遙晶法 (HVPE) ’在400〜ll〇〇°C之溫度環境下而形成；在此實施 例中’上述緩衝層11係使用MOCVD法形成。 另外’上述緩衝層11之材質係可選擇自：氮化錄 (GaN)、氣化銦鎵（inGaN)、氮化鋁鎵（AlGaN)、氮化銘銦 鎵（Alx InyGau_x_y)N，OSxSl ’OSySl)…等三族金屬氮化 在此實施例中’上述緩衝層11之材質係採用氮 物中之一 化鎵GaN < 接著’使用MBE法、HVPE法、或MOCVD法，在600V. Description of the invention (3) 11 ~ (gallium nitride) buffer layer; 12 ~ first epitaxial layer (gallium nitride thick epitaxial layer); 13 ~ second epitaxial layer / element structure. Embodiment: The main object of the present invention is to provide a method for manufacturing a Group III metal nitride which can improve the lattice mismatch between the Group III metal nitride epitaxial layer and the oxide substrate. FIG. 1 is a schematic cross-sectional view showing the structure of a second epitaxial layer / element structure, a first stupid layer, and a substrate in an embodiment of the present invention. Referring to Fig. 1 ', a method for manufacturing a group III metal nitride device according to the present invention includes the following steps. First, a buffer layer 11 (or a buffer film) is grown on an alumina substrate 10; wherein the buffer layer 11 is a group III metal nitride having a thickness greater than 05 / ζπ1. The above buffer layer 11 'uses a metal organic chemical vapor deposition method (MOCVD)' a molecular beam crystallizing method (jjbe) or a dentate chemical vapor phase telecrystallization method (HVPE) at a temperature of 400 to 100 ° C It is formed under the environment; in this embodiment, the above-mentioned buffer layer 11 is formed using a MOCVD method. In addition, the material of the above buffer layer 11 can be selected from: GaN, indium gallium (inGaN), aluminum gallium nitride (AlGaN), indium gallium nitride (Alx InyGau_x_y) N, OSxSl 'OSySl ), Etc. Group III metal nitrides In this embodiment, 'the material of the above buffer layer 11 is gallium nitride GaN < then' use MBE method, HVPE method, or MOCVD method, at 600
0626.5769TWF.ptd 第6頁0626.5769TWF.ptd Page 6
00 c之溫度環境下，再成長一第一蟲晶層（或厚蟲晶 12於上述氮化鎵緩衝層Η之上。在此實施例中，係使用具 有南成長速率優點之HVPE法’來成長上述第一磊晶層12。、 上述第一磊晶層12之材質可選擇自：氮化鎵（GaN)、 氮化銦鎵（InGaN)、氮化鋁鎵（A1GaN)、氮化鋁銦鎵 UlxInyGa(卜"）N，〇Sx$l …等三族金屬氮化物 中之一。在此實施例中，上述第一磊晶層12之材質係採用 氮化嫁GaN，厚度為1〇 /zm以上。 上述第一磊晶層（氮化鎵厚磊晶層）丨2 ,在未摻雜任何 雜質（impurity)下，經由霍爾量測，其載子濃度可達2 χ 1016 cnr3，載子移動速率可達1〇〇 cm/Vs以上。 最後’以上述第一磊晶層（氮化鎵厚磊晶層）丨2為基 底，使用MOCVD法，再形成第二磊晶層或元件結構（13)於 上述第一磊晶層12上。上述第二磊晶層13係為高品質之三 族金屬氮化物磊晶層’可依應用所需而作成單層結構、或 多層結構。上述元件結構1 3，例如為發光二極體（led)結 構，亦由MOCVD法來完成。 第2圖顯示氮化鎵厚磊晶層（第一磊晶層12)之光激光 頻譜圖。由圖可看出，其光譜之半寬高相當小，只有1〇 nm，且其黃色頻帶（Yellow band)訊號相當小。 第3圖顯示氮化鎵厚磊晶層（第一磊晶層12)之X光繞射 光譜圖。由圖可看出，其光譜之半高寬相當窄，只有150 arcsec，顯示依據本發明的方法所製造之薄膜品質相當 好。At a temperature of 00 c, a first worm crystal layer (or a thick worm crystal 12 is grown on the above gallium nitride buffer layer 上述. In this embodiment, the HVPE method with the advantage of a south growth rate is used to Grow the first epitaxial layer 12. The material of the first epitaxial layer 12 can be selected from: gallium nitride (GaN), indium gallium nitride (InGaN), aluminum gallium nitride (A1GaN), indium aluminum nitride Gallium UlxInyGa (Bu ") N, 0Sx $ l, etc. is one of the three group of metal nitrides. In this embodiment, the material of the first epitaxial layer 12 is nitrided GaN, and the thickness is 10%. Above / zm. The above first epitaxial layer (thick epitaxial layer of gallium nitride) 丨 2, without any impurity (impurity), through Hall measurement, its carrier concentration can reach 2 χ 1016 cnr3, The carrier movement rate can reach more than 100 cm / Vs. Finally, based on the above first epitaxial layer (thick GaN epitaxial layer) 2 and using MOCVD, a second epitaxial layer or element is formed. The structure (13) is on the first epitaxial layer 12. The second epitaxial layer 13 is a high-quality Group III metal nitride epitaxial layer. Into a single-layer structure or a multilayer structure. The above-mentioned element structure 13 is, for example, a light-emitting diode (LED) structure, and is also completed by the MOCVD method. Figure 2 shows a thick gallium nitride epitaxial layer (first epitaxial layer) 12) Light laser spectrogram. As can be seen from the figure, the full width at half maximum of its spectrum is quite small, only 10nm, and its yellow band signal is quite small. Figure 3 shows a thick gallium nitride epitaxial crystal X-ray diffraction spectrum of the first layer (first epitaxial layer 12). As can be seen from the figure, the FWHM of the spectrum is quite narrow, only 150 arcsec, indicating that the quality of the thin film produced according to the method of the present invention is quite good.
0626-5769TWF.ptd 第7頁 A59A〇50626-5769TWF.ptd Page 7 A59A〇5
族金屬氮化物元件 目前 用日亞化 方法，其 層與基板 匹配的問 傳統方式 匹配的問 雖然 限定本發 神和範圍 護範圍當 最常用 學公司 緩衝層 間因晶 題仍然 ，更能 題，對 本發明 明，任 内，當 視後附 所提出 只有0. 格常數 存在。 改善三 於光電 已以較 何熟悉 可做些 之申請 之方法。但是日亞化學公司提出之 Ml〜〇_5ym，未能有效隔絕磊晶 不同’而造成缺陷的廷伸，晶格不 因此’本發明之製造方法，相較於 族金屬氮化物磊晶層與基板晶格不 產業而言具有相當之實用性。 佳實施例揭露如上，然其並非用以 本項技藝者，在不脫離本發明之精 許之更動和潤飾，因此本發明之保 專利範圍所界定者為準。The group metal nitride element currently uses the Nichia method, and its layers match the substrate. Although the traditional method of matching is limited, the scope and scope of protection are limited. When the most commonly used company's buffer layer is still a crystal problem, it is more capable. The invention shows that, within the term, only 0. Lattice constants exist when viewed as attached. Improve Sanyu Optoelectronics is already familiar with some of the ways to make applications. However, the Ml ~ 〇_5ym proposed by Nichia Chemical Company failed to effectively isolate the defects caused by the epitaxial difference, and the crystal lattice does not therefore have the effect of the method of the present invention. Compared with the group metal nitride epitaxial layer and The substrate lattice is quite practical in terms of industry. The preferred embodiment is disclosed as above, but it is not used by the artist, and can be modified and retouched without departing from the essence of the present invention. Therefore, the scope of the patent protection of the present invention shall prevail.
0626-5769TW.ptd 第8頁0626-5769TW.ptd Page 8