TW472299B - III-V compound semiconductor - Google Patents

III-V compound semiconductor Download PDF

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TW472299B
TW472299B TW089103826A TW89103826A TW472299B TW 472299 B TW472299 B TW 472299B TW 089103826 A TW089103826 A TW 089103826A TW 89103826 A TW89103826 A TW 89103826A TW 472299 B TW472299 B TW 472299B
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compound semiconductor
pattern
scope
layer
melon
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TW089103826A
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Chinese (zh)
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Kazumasa Hiramatsu
Hideto Miyake
Takayoshi Maeda
Yasushi Iyechika
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Sumitomo Chemical Co
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    • H—ELECTRICITY
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    • 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
    • H01L33/02—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 characterised by the semiconductor bodies
    • H01L33/025—Physical imperfections, e.g. particular concentration or distribution of impurities
    • G—PHYSICS
    • G06—COMPUTING; CALCULATING OR COUNTING
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    • G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
    • G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
    • G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
    • G06F3/033—Pointing devices displaced or positioned by the user, e.g. mice, trackballs, pens or joysticks; Accessories therefor
    • G06F3/0354—Pointing devices displaced or positioned by the user, e.g. mice, trackballs, pens or joysticks; Accessories therefor with detection of 2D relative movements between the device, or an operating part thereof, and a plane or surface, e.g. 2D mice, trackballs, pens or pucks
    • G06F3/03543—Mice or pucks
    • G—PHYSICS
    • G06—COMPUTING; CALCULATING OR COUNTING
    • G06F—ELECTRIC DIGITAL DATA PROCESSING
    • G06F1/00—Details not covered by groups G06F3/00 - G06F13/00 and G06F21/00
    • G06F1/16—Constructional details or arrangements
    • G06F1/20—Cooling means
    • H—ELECTRICITY
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    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02367—Substrates
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    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02436—Intermediate layers between substrates and deposited layers
    • H01L21/02439—Materials
    • H01L21/02455—Group 13/15 materials
    • H01L21/02458—Nitrides
    • H—ELECTRICITY
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    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02518—Deposited layers
    • H01L21/02521—Materials
    • H01L21/02538—Group 13/15 materials
    • H01L21/0254—Nitrides
    • H—ELECTRICITY
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    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02612—Formation types
    • H01L21/02617—Deposition types
    • H01L21/0262—Reduction or decomposition of gaseous compounds, e.g. CVD
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02612—Formation types
    • H01L21/02617—Deposition types
    • H01L21/02636—Selective deposition, e.g. simultaneous growth of mono- and non-monocrystalline semiconductor materials
    • H01L21/02639—Preparation of substrate for selective deposition
    • H01L21/02642—Mask materials other than SiO2 or SiN
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02612—Formation types
    • H01L21/02617—Deposition types
    • H01L21/02636—Selective deposition, e.g. simultaneous growth of mono- and non-monocrystalline semiconductor materials
    • H01L21/02647—Lateral overgrowth
    • 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
    • H01L33/0075—Processes for devices with an active region comprising only III-V compounds comprising nitride compounds
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F04—POSITIVE - DISPLACEMENT MACHINES FOR LIQUIDS; PUMPS FOR LIQUIDS OR ELASTIC FLUIDS
    • F04D—NON-POSITIVE-DISPLACEMENT PUMPS
    • F04D25/00—Pumping installations or systems
    • F04D25/02—Units comprising pumps and their driving means
    • F04D25/08—Units comprising pumps and their driving means the working fluid being air, e.g. for ventilation
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01S—DEVICES USING THE PROCESS OF LIGHT AMPLIFICATION BY STIMULATED EMISSION OF RADIATION [LASER] TO AMPLIFY OR GENERATE LIGHT; DEVICES USING STIMULATED EMISSION OF ELECTROMAGNETIC RADIATION IN WAVE RANGES OTHER THAN OPTICAL
    • H01S5/00—Semiconductor lasers
    • H01S5/30—Structure or shape of the active region; Materials used for the active region
    • H01S5/32—Structure or shape of the active region; Materials used for the active region comprising PN junctions, e.g. hetero- or double- heterostructures
    • H01S5/323—Structure or shape of the active region; Materials used for the active region comprising PN junctions, e.g. hetero- or double- heterostructures in AIIIBV compounds, e.g. AlGaAs-laser, InP-based laser
    • H01S5/32308—Structure or shape of the active region; Materials used for the active region comprising PN junctions, e.g. hetero- or double- heterostructures in AIIIBV compounds, e.g. AlGaAs-laser, InP-based laser emitting light at a wavelength less than 900 nm
    • H01S5/32341—Structure or shape of the active region; Materials used for the active region comprising PN junctions, e.g. hetero- or double- heterostructures in AIIIBV compounds, e.g. AlGaAs-laser, InP-based laser emitting light at a wavelength less than 900 nm blue laser based on GaN or GaP

Abstract

Provided is a III-V compound semiconductor having a layer formed from a first III-V compound semiconductor expressed by the general formula InuGavAlwN (where 0 ≤ u ≤ 1, 0 ≤ v ≤ 1, 0 ≤ w ≤ 1, u+v+w=1), a pattern formed on the layer from a material different not only from the first III-V compound semiconductor but also from a second III-V compound semiconductor hereinafter described, and a layer formed on the first III-V compound semiconductor and the pattern from the second III-V compound semiconductor expressed by the general formula InxGayAlzN (where 0 ≤ x ≤ 1, 0 ≤ y ≤ 1, 0 ≤ z ≤ 1, x+y+z=1), wherein the full width at half maximum of the (0004) reflection X-ray rocking curve of the second III-V compound semiconductor is 700 seconds or less regardless of the direction of X-ray incidence. In the III-V compound semiconductor, which is a high quality semiconductor, the occurrence of low angle grain boundaries is suppressed.

Description

472299 A7 B7 五、發明說明（1 ) 發明背景 發明範圍 (請先閱讀背面之注意事項再填寫本頁) 本發明係關於以通式I n tl G a b A 1。N (其中a + b + c = l ’ OSa 各 1 ’ ， OSc 各 1)表 示的ΠΙ — V化合物半導體。 相關技藝的說明 以通式 I HaGabAlcN (其中 a + b + c = l， OSaSl，OSbSl，表示的皿一v 化 合物半導體可以作爲範圍由電磁光譜之紫外光區至可見光 區之高效率發光裝置的材料，因爲其相當於紫外光至紅光 的直接帶隙可藉改變第m族元素的組成而得到調整。除此 之外’因爲和S i及GaAs等常用的半導體相較，該等 化合物半導體具有大的帶隙，所以利用其在高溫下（此時 習知的半導體已無法運作）可以保持如半導體之性質的特 性，理論上應能製得具有極佳環境抗性的電子裝置。 經濟部智慧財產局員工消費合作社印製 然而，就該等化合物半導體而言，因爲其在接近熔點 時具有極高的蒸汽壓而極難成長出大的晶體，所以實用尺 寸的晶體（其可作爲供半導體裝置製造用的基材）即無法 製得。因此，在化合物半導體的製造中，藍寶石、S i C 、或者與化合物半導體具有類似晶體結構且能製得大的晶 體的其他材料常作爲化合物半導體外延成長於其上的基材 。使用此方法，具有相當良好品質之化合物半導體的晶體 得以製得。即使如此，因基材與化合物半導體間晶格常數 本紙張尺度適用_國國家標準（CNS)A4規格（210 X 297公釐） -4 - 472299 Α7 Β7 五、發明說明（2 ) 或熱擴散係數之差異而產生的晶體缺陷亦難以降低，並且 通常會有約1 0 8厘米-2或以上之缺陷密度的產生。 (請先閱讀背面之注意事項再填寫本頁) 另一方面，用以製得具有降低之缺陷密度的化合物半 導體之技術亦經披露，其使用具有如上所述之高晶體缺陷 密度的化合物半導體作爲基底（】pn . J . Appl . Phys .，Vol • 36,L899頁，1 997 )。即，高缺陷密度化合物半導體（在下 文中常稱爲基底晶體）係爲S i 〇2圖樣所覆蓋，而在其中 留下顯微開口，第二晶體成長（在下文中，第二晶體成長 可以稱爲再成長）並在彼之上實施。此方法的槪要將參考 _ 1作說明。 首先，於再成長的最初階段中，圖樣上未有晶體的成 長，晶體成長僅在開口中產生，即，產生選擇性成長。當 晶體成長自此階段持續進行時，各開口中的晶體成長會擴 展至整個圖樣，而得到將圖樣覆蓋於彼之下的結構。雖然 圖樣覆蓋之後步驟仍停留在再成長之晶體表面上，但是再 成長表面上的步驟會隨著晶體成長的進展而逐漸地平滑， 最後，即可得到平坦的晶體表面。 經濟部智慧財產局員工消費合作社印製 迄今，以下兩種方法據悉爲可行的方法其係藉上述內 埋結構的製造來降低化合物半導體中的晶體缺陷。此兩種 方法爲氫化物蒸汽相外延法（在下文中通常稱爲H V P E 法）及有機金屬蒸汽相外延法（在下文中通常稱爲 MOVPE法）。然而，該等方法涉及以下的問題。 首先，當其爲Η V Ρ Ε法時，習知成長於圖樣之上的 化合物半導體係以略微不同於基底晶體的角度定向而成長 -5- 本纸張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 472299 A7 B7 五、發明說明（3 ) 於開口之上的晶體則具有與基底晶體一致的晶體定向（472299 A7 B7 V. Description of the invention (1) Background of the invention (Please read the notes on the back before filling out this page) The present invention relates to the general formula I n tl G a b A 1. A II-V compound semiconductor represented by N (where a + b + c = l 'OSa each 1' and OSc each 1). The description of related techniques is based on the general formula I HaGabAlcN (where a + b + c = l, OSaSl, OSbSl, which is a compound semiconductor that can be used as a material for high-efficiency light-emitting devices ranging from the ultraviolet region of the electromagnetic spectrum to the visible region. , Because it is equivalent to the direct band gap of ultraviolet light to red light can be adjusted by changing the composition of group m elements. In addition, 'compared with commonly used semiconductors such as Si and GaAs, these compound semiconductors have A large band gap, so that it can maintain characteristics like semiconductors at high temperatures (at this time the conventional semiconductor can no longer operate), and in theory should be able to produce electronic devices with excellent environmental resistance. Ministry of Economic Affairs Wisdom Printed by the Consumer Cooperative of the Property Bureau. However, for these compound semiconductors, because of their extremely high vapor pressure near the melting point, it is extremely difficult to grow large crystals, so crystals of practical size (which can be used as semiconductor devices Manufacturing substrate)). Therefore, in the manufacture of compound semiconductors, sapphire, S i C Other materials that resemble a crystal structure and can produce large crystals are often used as substrates on which compound semiconductors are epitaxially grown. Using this method, crystals of compound semiconductors with fairly good quality are made. Even so, the substrate and The lattice constants between compound semiconductors are applicable to this paper size _ National Standard (CNS) A4 (210 X 297 mm) -4-472299 Α7 Β7 V. Crystal defects caused by the difference between the description of the invention (2) or the thermal diffusion coefficient It is also difficult to reduce, and usually there is a defect density of about 108 cm-2 or more. (Please read the precautions on the back before filling this page) On the other hand, it is used to make The technology of compound semiconductors is also disclosed, which uses a compound semiconductor having a high crystal defect density as described above as a substrate (] pn. J. Appl. Phys., Vol • 36, page L899, 1 997). That is, high defects The density compound semiconductor (hereinafter often referred to as the base crystal) is covered by the S i 〇2 pattern, leaving a microscopic opening in it, and the second crystal grows (below The second crystal growth can be called re-growth) and implemented on top of it. The method of this method will be explained with reference to 1. First, in the initial stage of re-growth, there is no crystal growth on the pattern. Growth only occurs in the openings, that is, selective growth. When crystal growth continues from this stage, the crystal growth in each opening will expand to the entire pattern, and a structure covering the pattern below it will be obtained. Although the pattern After covering, the steps remain on the surface of the re-growth crystal, but the steps on the re-growth surface will gradually smooth as the crystal grows, and finally, a flat crystal surface can be obtained. Employees' Cooperatives, Intellectual Property Bureau, Ministry of Economic Affairs To date, the following two methods are reported to be feasible methods, which are to reduce the crystal defects in compound semiconductors by manufacturing the above-mentioned embedded structure. These two methods are a hydride vapor phase epitaxy method (hereinafter commonly referred to as the H V P E method) and an organometal vapor phase epitaxy method (hereinafter commonly referred to as the MOVPE method). However, these methods involve the following problems. First of all, when it is the Η V Ρ Ε method, the compound semiconductor that is conventionally grown on the pattern grows at an angle orientation slightly different from that of the base crystal. -5- This paper size applies the Chinese National Standard (CNS) A4 specification. (210 X 297 mm) 472299 A7 B7 V. Description of the invention (3) The crystal above the opening has a crystal orientation consistent with the base crystal (

Appl. Phys. Leu.，Vol. 73,48 1 頁，1 998 )。因此，成長 於圖樣之上的晶體與成長於開口之上的晶體在晶體定向上 並不一致’其界面形成所謂的低角度晶界其中內含許多邊 緣位錯。當再成長之晶體的厚度增加時，晶體定向逐漸趨 於一致’但是未發生邊緣位錯的膜厚必須爲約6 〇微米或 以上。此種厚膜的成長不僅耗費許多時間，並且亦會發生 因爲再成長晶體與基底晶體間熱擴散係數的差異而使得變 形增加的問題。基材的內部變形會引發基材的形變，此又 使得晶體成長產生問題，並因此引發習見半導體製程中的 製造問題。 本發明之目的係提供瓜一 V化合物半導體其中低角度 晶界的發生受到抑制。 發明槪述 本發明係關於（1 ) ΙΠ — V化合物半導體其具有以通 式 I nuGavAlwN (其中 OSuSl ，OSvSl ， OSw各1 ，u + v+ w= l)表示之第一個ΙΠ — V化合 物半導體形成的層，由不同於第一個m — V化合物半導體 且不同於下文中提及之第二個ΙΠ — V化合物半導體之材料 形成於層上的圖樣，及以通式I nxGayA 1ZN (其中 O^x^l - O^y^l - O^z^l > x + y + z = l )表示之第二個in— V化合物半導體在第一個m — V化合 物半導體及圖樣上形成的層，其中第二個m — V化合物半 (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 I II - II ^ ---I I---I I I I I ! I - I — — — — — — —— — I — — — — — — 本纸張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -6- 472299 A7 B7 五、發明說明（4 ) 導體之（0 0 0 4 )反射X -光擺動曲線最大値一半處的 全寬爲7 0 0秒或以下（不論X —光入射的方向爲何）。 本發明亦係關於（2 ) m — v化合物半導體其具有以 通式 I nuGa'. AlwN (其中 OSuSl ，0SVS1 ，OSwSl ，u + v+ w=l)表示之第一個瓜一V化 合物半導體形成的層，由不同於第一個瓜一V化合物半導 體且不同於下文中提及之第二個皿一V化合物半導體之材 料形成於層上的圖樣，及以通式I η X G a y A 1 z N (其 中 0 盔 xSl ，，OSzSl ，x + y + z = 1 )表示之第二個ΠΙ — V化合物半導體在第一個ΠΙ — V化 合物半導體及圖樣上形成的層，其中圖樣的上表面不與第 二個]Π — V化合物半導體接觸。 除此之外，本發明亦係關於如（1 )或（2 )中所述 的I[[一 V化合物半導體，其中圖樣係由W (鎢）形成。本 發明所涵蓋之半導體裝置及電子裝置的實例有發光二極體 (LED)、雷射二極體（L D )等，但不限於彼。 附圖槪述 圖1係顯示再成長如何依據先前技藝在圖樣上進行的 圖形。 圖2 A及2 B提供以不同方向入射至實例1與比較例 1中之圖樣條紋之X —光擺動曲線的圖形（平行一圖2 A ;垂直一圖2 B )。 使用於圖1中的符號如下。 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） (請先閱讀背面之注咅？事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 ------II 訂------------------------------ 472299 A7Appl. Phys. Leu., Vol. 73, 48 p. 1, 998). Therefore, the crystals grown on the pattern and the crystals grown on the openings do not have the same crystal orientation ', and their interfaces form so-called low-angle grain boundaries, which contain many edge dislocations. When the thickness of the regrown crystal is increased, the crystal orientation gradually becomes uniform ', but the film thickness where edge dislocation does not occur must be about 60 microns or more. The growth of such a thick film not only takes a lot of time, but also causes a problem that the deformation increases due to the difference in thermal diffusion coefficient between the regrown crystal and the base crystal. The internal deformation of the substrate can cause deformation of the substrate, which in turn causes problems with crystal growth, and thus causes manufacturing problems in conventional semiconductor processes. An object of the present invention is to provide a melon-V compound semiconductor in which occurrence of low-angle grain boundaries is suppressed. DESCRIPTION OF THE INVENTION The present invention relates to (1) a Π-V compound semiconductor having the first Π-V compound semiconductor represented by the general formula I nuGavAlwN (where OSuSl, OSvSl, and OSw each 1, u + v + w = l). A layer formed of a material different from the first m-V compound semiconductor and different from the second II-V compound semiconductor mentioned below, and a pattern of the general formula I nxGayA 1ZN (where O ^ x ^ l-O ^ y ^ l-O ^ z ^ l > x + y + z = l) The second in-V compound semiconductor layer formed on the first m-V compound semiconductor and pattern Among them, the second m — V compound is half (please read the precautions on the back before filling out this page) Printed by I II-II ^ --- I I --- IIIII! I — — — — — — — — — I — — — — — — This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) -6- 472299 A7 B7 V. Description of the invention (4) The total width of the (0 0 0 4) reflected X-ray swing curve at the maximum half of the conductor is 700 seconds or less (not On X — what is the direction of light incidence). The present invention also relates to a (2) m-v compound semiconductor having the first melon-V compound semiconductor formed by the general formula I nuGa '. AlwN (where OSuSl, OSVS1, OSwSl, u + v + w = 1). Layer, a pattern formed on the layer from a material different from the first cu-V compound semiconductor and different from the second cu-V compound semiconductor mentioned below, and with the general formula I η XG ay A 1 z N (Where 0 helmet xSl, OSzSl, x + y + z = 1) is a layer formed by the second III-V compound semiconductor on the first III-V compound semiconductor and the pattern, wherein the upper surface of the pattern does not correspond to Second] Π—V compound semiconductor contact. In addition, the present invention also relates to I [[-V compound semiconductor as described in (1) or (2), wherein the pattern is formed of W (tungsten). Examples of semiconductor devices and electronic devices covered by the present invention include, but are not limited to, light emitting diodes (LEDs), laser diodes (L D), and the like. Brief Description of the Drawings Figure 1 is a diagram showing how re-growth is performed on a pattern according to the prior art. Figures 2A and 2B provide X-ray swing curves of the pattern fringe incident in Example 1 and Comparative Example 1 in different directions (parallel-FIG. 2A; vertical-FIG. 2B). The symbols used in FIG. 1 are as follows. This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) (Please read the note on the back? Matters before filling out this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs ------ Order II ------------------------------ 472299 A7

五、發明說明（5 ) 經濟部智慧財產局員工消費合作社印製 1 :由第一個m — v化合物半導體形成的層（基底層 ) 2:由不同於第一個及第二個瓜一v化合物半導體之 材料形成的圖樣 3 :由第二個瓜一v化合物半導體形成的層（再成長 層） 發明詳述 使用於本發明之半導體中的m—v化合物半導體其特 徵在於第二個m — v化合物半導體之（〇 〇 〇 4 )反射χ -光擺動曲線最太値一半處的全寬爲7 0 0秒或以下（不 論X —光入射的方向爲何）。 除此之外，本發明的特徵在於由不同於第一個]π_v 化合物半導體及第二個m—ν化合物半導體之材料形成之 圖樣的上表面幾乎不和成長於圖樣之上的晶體接觸。雖然 目即原因不明，但是咸信當圖樣不和再成長於其上的晶體 接觸時低角度晶界的發生會受到抑制。 在某些先前的實例中，孔隙會在圖樣上形成，医I 圖 樣與再成長層間會生成間隙，然而即使在該等情況中，孔 隙亦會在所謂的過度成長之後（即，再成長層係或多或少· 過度成長至與圖樣接觸之後）形成。相較而言，本發日月之 特徵在於再成長層的過度成長幾乎不會出現在圖樣上。 本發明之更詳細的說明將示於以下。 化合物半導體再成長期間具有某些耐久度的材料_ ^ n n n ϋ J— 1· ϋ n I ,β, - n I i I ϋ )aJ I ^ n I I n n I (請先閱讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -8- 472299 A7 B7 五、發明說明（6 ) (請先閱讀背面之注意事項再填寫本頁) 合作爲使用於本發明中之圖樣的材料。即，在有圖樣生成 於其上之樣品上的再成長開始之前，如果材料會因蒸發作 用而消散或者會在再成長氣壓中或再成長溫度下因熔化而 變形，則所欲的再成長難以在良好的生產量下實施。然而 ，因爲再成長層不會在本發明之圖樣上過度地成長，所以 圖樣表面的粗糙化，與基底層的分離等至少在再成長的最 初階段中不會發生，並且本發明之效果不會顯著地受到損 害。 更特定言之’樣品在再成長期間係曝於諸如氨的氣壓 下，並且可在該等條件下使用的材料包括諸如W (鎢）、 Re (銶）、Mo (鉬）、Cr (鉻）、Co (銘）、V. Description of the invention (5) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 1: layer formed by the first m-v compound semiconductor (substrate layer) 2: different from the first and second melon v Pattern 3 made of material of compound semiconductor: Layer (re-grown layer) formed by the second melon-v compound semiconductor Detailed description of the invention The m-v compound semiconductor used in the semiconductor of the present invention is characterized by the second m- v The compound semiconductor's (00004) reflection x-light swing curve has a full width at the maximum half of 700 seconds or less (regardless of the direction of X-light incident). In addition, the present invention is characterized in that the upper surface of the pattern formed of a material different from the first] π_v compound semiconductor and the second m-ν compound semiconductor hardly contacts the crystal grown on the pattern. Although the immediate cause is unknown, Xianxin believes that the occurrence of low-angle grain boundaries will be suppressed when the pattern is not in contact with the crystals grown on it. In some previous examples, pores were formed on the pattern, and gaps were created between the I-pattern and the re-grown layer, but even in these cases, the pores were More or less · overgrowth after contact with the pattern). In contrast, the feature of this Sun and Moon is that the excessive growth of the re-growth layer hardly appears on the pattern. A more detailed description of the present invention will be shown below. Materials with certain durability during compound semiconductor growth_ ^ nnn ϋ J— 1 · ϋ n I, β,-n I i I ϋ) aJ I ^ n II nn I (Please read the precautions on the back before filling (This page) This paper size is applicable to Chinese National Standard (CNS) A4 (210 X 297 mm) -8- 472299 A7 B7 V. Description of the invention (6) (Please read the precautions on the back before filling this page) Cooperation is The pattern material used in the present invention. That is, before the re-growth of a sample on which a pattern is generated is started, if the material dissipates due to evaporation or is deformed by melting under re-growth pressure or re-growth temperature, the desired re-growth is difficult Implemented with good throughput. However, because the re-grown layer does not grow excessively on the pattern of the present invention, roughening of the pattern surface, separation from the base layer, and the like do not occur at least in the initial stage of re-growth, and the effect of the present invention does not Significantly damaged. More specifically, 'samples are exposed to atmospheric pressure such as ammonia during re-growth, and materials that can be used under such conditions include materials such as W (tungsten), Re (rhenium), Mo (molybdenum), Cr (chromium) , Co (ming),

Si ( W )、金、Z r (錯）、T a (鉬）、T i (駄） 、N b (鈮）、鎳、鉑、V (釩）、H f (給）、及 P d (鈀）等元素，以及諸如B N (氮化硼）與包括諸如 S i 3 N 4的S i N x (氮化矽）等化合物，及諸如氮化鎢 、氮化鈦、氮化銷、氮化給、氮化釩、氮化鈮、氮化鉬、 氮化鉻、氮化鉬、氮化銶、氮化鐵等氮化物。 經濟部智慧財產局員工消費合作社印製 至少兩層之壓層的圖樣（其中壓層中的接觸層係由彼 此相異的材料製成）可於本發明中使用。特定言之，圖樣 的壓層可以包括由W製成的層與除了 W之外的材料製成的 層。此外，使用彼不易製得本發明之結構的材料（例如 S i 〇2)或者在再成長條件下呈現不安定的材料均可作爲 壓層中不同於W之層的材料。 先前習知的圖樣幾何形狀可用於本發明之圖樣。特定 -9 - 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 472299 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明說明（7 ) 實例包括槪稱爲線/空間圖樣的圖樣其中預定寬度的條紋 彼此平行排列’一者與另一者間以預定寬度的開口分隔’ 以及經由圓形或多邊形開口使基底層部份曝光的圖樣。該 等圖樣幾何形狀可依再成長條件，圖樣材料等選用。 當其爲線/空間圖樣時，圖樣寬度最好不小於 0 . 0 5微米且不大於2 0微米。如果圖樣寬度小於 0 · 0 5微米，則本發明降低缺陷密度之效果將會不足。 另一方面’如果其大於2 0微米，則埋設圖樣所需的時間 又變得太長而不實際。基於相同的理由，當其爲具有圓形 或多邊形開口的圖樣時，開口間的距離最好不小於 0 · 05微米且不大於2 0微米。 當其爲線/空間圖樣時，空間（基底層經由彼被施以 曝光的開口）的寬度最好不小於〇 . 〇 1微米且不大於 2 0微米。如果空間寬度小於〇 . 〇 1微米，則對目前的 半導體製程而言，實用上精確的形狀將難以得到，因此並 不適宜。另一方面，如果其大於2 0微米，則本發明降低 缺陷密度之效果將會不足。基於相同的理由，當其爲具有 圓形或多邊形開口的圖樣時，開口尺寸最好不小於 0.01微米且不大於20微米。 當其爲線/空間圖樣幾何形狀時，條紋方向未有特別 的限制’但是因再成長而使得缺陷降低的效果有時會依條 紋方向而改變。在該等情況中，適宜的方向可依圖樣幾何 形狀、圖樣材料、再成長條件等而選用。 蒸發 '濺射、化學蒸鍍（CVD)，或者電鍍等習知 (請先閱讀背面之注意事項再填寫本頁) (M- 線_ 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -10- 經濟部智慧財產局員工消費合作社印製 472299 A7 B7 五、發明說明（8 ) 的技術可用於圖樣的形成。化合物材料的圖樣亦可在化學 反應之前藉形成之膜的化學反應而形成。此技術的實例係 藉包括热之氣壓中之錫Μ吳的退火而形成氮化鑛膜。圖樣的 膜厚可由實際的耐久性及生產量決定。當其爲W時，厚度 不小於2 n m且不大於5微米。 HV P E法或MO V P E法可以作爲本發明中用於再 成長之晶體成長的方法。Η V P E法可以具優勢的方式使 用於本發明中因爲其可以提供高成長率並且可以在短時間 內製得良好的晶體。Μ Ο V Ρ Ε法亦可以具優勢的方式使 用於本發明中因爲均勻的晶體成長可在多種基材上實施。 再成長的條件包括溫度、壓力、載氣、及原料。習知 的條件可用於再成長。更特定言之，如果I η不爲構成元 素’則再成長溫度最好不低於6 0 0 °C且不高於1 2 0 0 °C，雖然其視欲成長之化合物半導體的性質而定。如果再 成長溫度低於6 0 0 °C或高於1 2 0 0 °C，則良好的晶體 難以藉再成長而製得。此外，如果化合物半導體含有I η 作爲構成元素，因其熱安定性會崩解，所以再成長溫度最 好不低於6 0 0 °C且不高於9 0 0 °C。 可用於本發明中之再成長的成長壓力不低於1 〇 〇 P a。如果供再成長用的壓力低於1 〇 〇 P a ，則良好 的晶體難以製得。壓力最好爲500 Pa或以上，並以 1 0 0 0 P a或以上爲更佳。結晶度有隨成長壓力增加 而改善的傾向，但是一般而言，供晶體成長用的 MOVPE設備或者HVPE設備在工業上不以極高的成 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -11 - (請先閱讀背面之注意事項再填寫本頁) -1 I 1 —塞 — — —— —— — — — — — — — — 472299 Α7 Β7 —----- 五、發明說明（9 ) 長壓力使用；因此’供再成長用的成長壓力最好爲10大 氣壓或以下。 可用於本發明中之再成長的載氣包括氫氣、氮氣、氦 氣、氬氣等’其習用於MOV P E或HV P E中。 以下的原料可藉MOV P E法用於本發明之瓜一V化 合物半導體的製造。 可用的第ΙΠ族材料包括：以通式RiRzRsG a袠示 的三烷基鎵（其中R i、R 2、及R 3表示低碳烷基），例 如三甲基鎵〔（CH3)3Ga ，在下文中常以TMG表示 〕及三乙基鎵〔（C2H5)3Ga，在下文中常以TEg 表示〕；以通式RiRzRaAl表示的三烷基鋁（其中 、R2、及R3表示低碳烷基），例如三甲基鋁〔（ CH3) 3A i〕及三乙基鋁〔（C2Hs) 3A 1 ，在下文 中常以T E A表示〕；三甲基aminealane〔 （ C Η 3 ) 3 n :A 1 Η 3 ):及以通式RiRsRaln表示的三烷基絪（ 其中Ri、R2、及R3表示低碳烷基），例如三甲基 (CH3)3In，在下文中常以TMI表示〕。該等材料 係單獨使用或者以其組合使用。 第V族材料包括諸如銨、肼、甲基肼、1 ，1 —二甲 基肼、1，2 —二甲基肼、第三丁胺、及乙二胺。該等材 料係單獨使用或者以其組合使用。在該等材料中，銨及肼 較具優勢因爲該等元素不含碳原子所以可使半導體的碳污 染最小化，並且銨爲更佳者因爲其易於處理。 s i 、Ge '或0係作爲供IE — V化合物半導體用的 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） C請先閱讀背面之、注意事項再填寫本頁} 經濟部智慧財產局員工消費合作社印製 -------訂---------線！ ----------------------- -12- 經濟部智慧財產局員工消費合作社印製 472299 A7 五、發明說明（10 ) η -型摻雜劑。在該等摻雜劑中，s i爲較佳者，因爲其 容易製得低電阻η ~型材料此外亦因爲高純度的原料可以 取得。可用於S i摻雜的原料包括矽烷（s 1 Η 4 )、乙矽 ^ ( S i 2 Η 6 )、及一甲基矽烷（Si (CH3)H3)等 〇 以下原料可藉HVP E法而用於本發明之瓜一V化合 物半導體的製造。 氯化氫氣體分別和金屬G a及I η反應可製得作爲第 瓜族材料的GaCl及InCl °GaCl及InCi亦 可以利用氯化氫氣體在高溫下和以下化合物反應而製得， 即’以通式R1R2R3G a表市的二院基嫁（其中R_i、 R2、及R3表示低碳烷基），例如TMG或TE G，及以 通式RiRsRs I η表示的三烷基銦（其中Ri、R2、及 R 3表示低碳烷基），例如Τ Μ I或三乙銦。除此之外，氯 化二甲基鎵（Ga (CH3)2C1)、氯化二乙基鎵（Si (W), gold, Z r (wrong), T a (molybdenum), T i (駄), N b (niobium), nickel, platinum, V (vanadium), H f (g), and P d ( Elements such as palladium), and compounds such as BN (boron nitride) and compounds including Si N x (silicon nitride) such as Si 3 N 4 and tungsten nitride, titanium nitride, nitride pin, nitride Nitrogen, such as vanadium nitride, niobium nitride, molybdenum nitride, chromium nitride, molybdenum nitride, hafnium nitride, iron nitride. At least two layers of laminates printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs (where the contact layers in the laminates are made of different materials) can be used in the present invention. In particular, the laminated layer of the pattern may include a layer made of W and a layer made of a material other than W. In addition, the use of materials (such as Si02) which are difficult to obtain the structure of the present invention, or materials which exhibit instability under re-growth conditions can be used as materials of layers other than W in the laminate. Previously known pattern geometries can be used in the patterns of the present invention. Specific-9-This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 472299 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (7) Examples include the so-called line / The pattern of the spatial pattern is a pattern in which stripes of a predetermined width are arranged in parallel with each other, 'one is separated from another by an opening of a predetermined width', and a pattern in which the base layer is partially exposed through a circular or polygonal opening. These pattern geometries can be selected according to the growth conditions and pattern materials. When it is a line / space pattern, the width of the pattern is preferably not less than 0.05 μm and not more than 20 μm. If the pattern width is less than 0.5 μm, the effect of reducing defect density of the present invention will be insufficient. On the other hand, if it is larger than 20 micrometers, the time required to bury the pattern becomes too long and impractical. For the same reason, when it is a pattern with circular or polygonal openings, the distance between the openings is preferably not less than 0. 05 microns and not more than 20 microns. When it is a line / space pattern, the width of the space (the base layer via the opening to which it is exposed) is preferably not less than 0.01 μm and not more than 20 μm. If the space width is less than 0.01 micron, a practically accurate shape will be difficult to obtain for current semiconductor processes, and therefore it is not suitable. On the other hand, if it is larger than 20 µm, the effect of reducing the defect density of the present invention will be insufficient. For the same reason, when it is a pattern having a circular or polygonal opening, the opening size is preferably not less than 0.01 m and not more than 20 m. When it is a line / space pattern geometry, there is no particular limitation on the direction of the stripes', but the effect of reducing defects due to re-growth sometimes changes depending on the direction of the stripes. In these cases, the appropriate direction can be selected depending on the pattern geometry, pattern material, and re-growth conditions. Evaporation, sputtering, chemical vapor deposition (CVD), or electroplating (please read the precautions on the back before filling this page) (M-line_ This paper size applies to China National Standard (CNS) A4 specifications (210 X 297 mm) -10- Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 472299 A7 B7 5. The technology of the invention description (8) can be used to form the pattern. The pattern of the compound material can also be borrowed from the formed film before the chemical reaction. It is formed by chemical reaction. An example of this technique is the formation of a nitrided ore film by annealing including tin in the hot air pressure. The film thickness of the pattern can be determined by the actual durability and throughput. When it is W, the thickness Not less than 2 nm and not more than 5 microns. The HV PE method or MO VPE method can be used as a method for crystal growth in the present invention. Η The VPE method can be used in the present invention in an advantageous manner because it can provide high The growth rate can also produce good crystals in a short time. The MV V PP method can also be used in an advantageous manner in the present invention because uniform crystal growth can be implemented on a variety of substrates. Conditions include temperature, pressure, carrier gas, and raw materials. Conventional conditions can be used for re-growth. More specifically, if I η is not a constituent element, the re-growth temperature is preferably not lower than 60 ° C and not more than Above 1 2 0 ° C, although it depends on the nature of the compound semiconductor to be grown. If the re-growth temperature is lower than 6 0 ° C or higher than 1 2 0 ° C, it is difficult to borrow good crystals It is made by growing. In addition, if the compound semiconductor contains I η as a constituent element, it will disintegrate due to its thermal stability. Therefore, the re-growth temperature is preferably not lower than 600 ° C and not higher than 900 ° C. The growth pressure that can be used for re-growth in the present invention is not less than 1000 Pa. If the pressure for re-growth is less than 1000 Pa, good crystals are difficult to produce. The pressure is preferably 500 Pa or Above, it is more preferable to be 100 Pa or more. The crystallinity tends to improve as the growth pressure increases, but in general, MOVPE equipment or HVPE equipment for crystal growth is not extremely high in industry. The cost paper size applies to China National Standard (CNS) A4 (210 X 297 male) ) -11-(Please read the precautions on the back before filling out this page) -1 I 1 —plug — — — — — — — — — — — 472299 Α7 Β7 —----- 5. Description of the invention (9) Long pressure use; therefore, 'the growth pressure for re-growth is preferably 10 atmospheres or less. The carrier gas that can be used for re-growth in the present invention includes hydrogen, nitrogen, helium, argon, etc.', which is commonly used MOV PE or HV PE. The following raw materials can be used in the production of the melon-V compound semiconductor of the present invention by the MOV PE method. Useful Group III materials include: trialkylgallium (where Ri, R2, and R3 represent lower alkyl groups) represented by the general formula RiRzRsG a, such as trimethylgallium [(CH3) 3Ga, in In the following, it is often represented by TMG] and triethylgallium [(C2H5) 3Ga, often in the following TEg]]; trialkylaluminum represented by the general formula RiRzRaAl (wherein, R2 and R3 represent lower alkyl groups), such as Trimethylaluminum [(CH3) 3A i] and triethylaluminum [(C2Hs) 3A 1, often referred to as TEA below]; trimethylaminealane [(C Η 3) 3 n: A 1 Η 3): And trialkylfluorene represented by the general formula RiRsRaln (wherein Ri, R2, and R3 represent lower alkyl groups), such as trimethyl (CH3) 3In, which is often referred to as TMI hereinafter]. These materials are used alone or in combination. Group V materials include, for example, ammonium, hydrazine, methylhydrazine, 1,1-dimethylhydrazine, 1,2-dimethylhydrazine, tertiary butylamine, and ethylenediamine. These materials are used alone or in combination. Among these materials, ammonium and hydrazine have advantages because these elements do not contain carbon atoms, which can minimize the carbon pollution of semiconductors, and ammonium is better because it is easy to handle. si, Ge 'or 0 are used as standard for this paper for IE-V compound semiconductors. Applicable to China National Standard (CNS) A4 (210 X 297 mm). C Please read the notes on the back before filling in this page} Economy Printed by the Ministry of Intellectual Property Bureau's Consumer Cooperatives ------- Order --------- Line! ----------------------- -12- Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 472299 A7 V. Description of the invention (10) η-type doping Agent. Among these dopants, s i is preferred because it is easy to produce low-resistance η-type materials and also because high-purity raw materials can be obtained. The raw materials that can be used for Si doping include silane (s 1 Η 4), ethyl silicon ^ (S i 2 Η 6), and monomethyl silane (Si (CH3) H3). The following raw materials can be obtained by the HVP E method. It is used in the manufacture of melon-V compound semiconductor of the present invention. The reaction of hydrogen chloride gas with metals G a and I η can be used to prepare GaCl and InCl, which are Group III materials. GaCl and InCi can also be prepared by reacting hydrogen chloride gas with the following compounds at high temperature, namely Tables of the two hospitals (where R_i, R2, and R3 represent lower alkyl groups), such as TMG or TEG, and trialkylindium represented by the general formula RiRsRs I η (where Ri, R2, and R 3 Stands for lower alkyl), such as TIM or triethylindium. In addition, dimethylgallium chloride (Ga (CH3) 2C1), diethylgallium chloride (

Ga (C2H5)2C1)'氯化二甲基銦（ I n ( C Η 3 ) 2 C 1 )、氯化二乙基銦（ I n ( C 2 Η 5 ) 2 C 1 )，或類似物可在高溫下分解而製 得GaCl及InCl。將載氣氣泡供應至諸如GaCi2 、I nC丨2 (其在常溫下呈現安定）中亦爲可行。其可以 單獨使用或者組合使用。 第V族材料包括諸如銨、肼、甲基腓、1，1 一二甲 基肼、1 ，2 -二甲基肼、第三丁胺、及乙二胺。該等材 料係單獨使用或者以其組合使用。在該等材料中，銨及肼 t紙張尺巾酬家標準(CNS)A4規格（210 X 297公釐〉 -13- ------!--------- i ---1--1 1 訂·！- (請先閱讀背面之注音？事項再填寫本頁) 472299 Γ Α7 ___— Β7 五、發明說明扣) 較具優勢因爲該等元素不含碳原子所以可使半導體的碳污 染最小化’並且銨爲更佳者因爲其易於處理。 (請先閱讀背面之注意事項再填寫本頁) S i 、G e、或0係作爲供瓜一 V化合物半導體用的 η -型摻雜劑。在該等摻雜劑中，s i爲較佳者，因爲其 容易製得低電阻η -型材料此外亦因爲高純度的原料可以 取得。可用於S i摻雜的原料包括諸如一氯砂院（ SiHsCl)及二氯矽烷（SiH2Cl2)。 經濟部智慧財產局員工消費合作社印製 在本發明中，有時會發生再成長之後凹陷在第一個皿 一 V化合物半導體之層的表面中形成的現象，其視圖樣製 造條件及再成長條件而定。使用以通式 I nuGavAlwN (〇^u<l > Ο ^ v < 1 ，〇<w SI，u + v+ w=l)表示的ΠΙ — V化合物半導體作爲 第一個m — v化合物半導體有時可以抑制此凹陷的形成。 在特定條件中，A 1 N組成比（以上通式中w的値）爲1 %或以上，並以5 %或以上爲較佳。在特定條件中，第一 個皿一V化合物半導體層的厚度爲〇 . 3nm或以上，並 以1 n m或以上爲較佳。一般而言，再成長期間抑制凹陷 形成的效果會隨A 1 N組成比或第一個ID -V化合物半導 體層之厚度的增加而增加，但是同其時，第一個瓜一 V化 合物半導體的結晶度會有降低的傾向；因此第一個m — V 化合物半導體層的厚度必須依據A 1 N組成比施以調整。 實例 實例1，比較例1 -14 - 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 472299 A7 B7 五、發明說明（12 ) (請先閱讀背面之注意事項再填寫本頁) 首先，以如下的方式製得基底晶體。使用M 0 v P E 法，G a N的緩衝層在5 5 0 °C下以5 0 n m _的厚度成長 於藍寶石基材上，並且G a N在約1 1 〇 〇°C下進一·步成 長至4微米之厚度。然後，利用濺射將W以3 0 n m的厚 度澱積在基底晶體上，並利用習知的攝影刻印術形成具有 5 -微米開口及5 _微米條紋的條紋圖樣。條紋方向爲< 1 — 1 0 0 >方向。然後，使用此晶體，以Η V P E法實 施再成長至3 3微米的厚度。此外，以S i 0 2替代W形成 圖樣並作爲第一比較例，並且再成長係以相同的方式實施 。在任一個例子中，藉再成長製得的晶體具有如鏡般的表 面。 爲檢視由是製得的晶體在定向上的變異，X —光擺動 曲線係以平行及垂直於條紋方向的方向量測。圖2 A及 經濟部智慧財產局員工消費合作社印製 2 B顯示其結果。當再成長係於W圖樣上實施時，擺動曲 線最大値一半處的全寬恆定在2 0 0秒或以下，不論X -光入射的方向爲何，並且在晶體定向中未觀察到變異。另 一方面，當其爲S i 0 2圖樣時（比較例），平行於圖樣條 紋之方向的擺動曲線其最大値一半處的全寬爲狹窄，但是 在垂直於條紋的方向，最大値一半處的全寬增加至7 5 0 秒或以上（見圖2 B )。此意味相對於基底晶體而言圖樣 上的晶體再成長具有晶體定向上的變異並且與W圖樣的情 況相較其結晶度不足。 將第一實例中製得的樣品沿垂直於圖樣的方向施以劈 裂，並在透射電子顯微鏡下觀察其截面積以確認再成長膜 >紙張尺度適用中國國家標準（CNS)A4規格⑵〇 X 297公髮) Γ-Ι5 - 472299 A7 I____-__B7 五、發明說明（13 ) 未過度成長於W圖樣上。 實例2 (請先閱讀背面之注意事項再填寫本頁) 依據本發明之具有降低之缺陷的G a a〖N膜係以等 同於第一實例的方式藉再成長在具有條紋圖樣的圖樣上形 成。適宜的層係於G a A 1 N膜之上形成，並且半導體製 程（例如餓刻及電積）被重覆地施行以製得電子裝置例如 HEMTs (高電子遷移晶體管）或者feTs (電場效 應晶體管）。該等電子裝置具有極佳的電性及信賴性因爲 內含於晶體中作爲裝置之機能的晶體缺陷之數目得以降低 〇 實例3 經濟部智慧財產局員工消費合作社印製 依據本發明之具有降低之缺陷的G a A 1 N膜係以等 同於第一實例的方式藉再成長在具有條紋圖樣的圖樣上形 成。在此G a A 1 N膜之上形成η —型層，具有之帶隙較 η -型層者爲小的層（發光層），及Ρ —型層，各層係由 上述順序的化合物半導體形成，並且半導體製程（例如蝕 刻及電積）被重覆地施行以製得發光裝置例如發光二極體 (LED)或者半導體雷射（LD)。該等發光裝置具有 極佳的發光特性及信賴性’特佳的壽命，因爲內含於晶體 中作爲裝置之機能的晶體缺陷之數目得以降低。 實例4 G a N係以等同於第一實例的方式成長至4微米之厚 本紙張尺度適用士國國家標準（CNS)A4規格（2i0x 297公釐） 472299 A7 _______ B7 五、發明說明（14 ) 度’並有GaA1N成長於其上。此層的a1N組成比爲 約1 5 % ’且厚度爲3 0 n m。利用電子束蒸鍍法在此 層之上形成W之2 0 - n m厚膜，並以習知的攝影刻印術 形成條紋圖樣。條紋方向爲< 1 1 〇 〇 >方向，並且條 紋寬度及條紋間隔均爲5微米。然後，以Μ Ο V P E法實 施再成長。成長壓力爲40 k Pa ，並且再成長層的厚 度爲3微米。藉再成長製得的結晶具有如鏡般的表面。將 第一及第四實例中製得的樣品沿垂直於條紋圖樣的方向施 以劈裂’並在透射電子顯微鏡下觀察其截面積；結果顯示 雖然在第一實例中製得之樣品的基底晶體上偶有損壞的現 象’但是在第四實例中製得之樣品的基底晶體上則無損壞 的現象。 實例5 G a N係以等同於第一實例的方式成長至4微米之厚 度。利用濺射將S i 0 2膜以5 0至7 0 n m的厚度澱積 在此基底晶體上，再利用濺射將鎢（W )膜以5 0 n m 的厚度澱積在其上。然後，利用習知的攝影刻印術，在彼 上形成條紋圖樣。條紋方向爲< 1 一 1 〇 0 >及< 1 1 — 2 0>方向。然後，以低壓MOVPE法實施再成長。再 成長膜的厚度爲約8微米。將由是製得的樣品及第一實例 中製得的樣品沿垂直於條紋圖樣的方向施以劈裂，並在透 射電子顯微鏡下觀察其截面積；結果顯示雖然在第一實例 之樣品上觀察到凹陷在掩模下形成，但是在第五實例中製 (請先閱讀背面之注意事項再填寫本頁) •-------訂--- ----— 線― 經濟部智慧財產局員工消費合作社印製 本紙張尺度適用中國國家標準（CNS>A4規格（210 x 297公釐） -17 - 472299 ---------- B7_______ 五、發明說明（15 ) 得的樣品上則發現凹陷的形成被大量地降低。 實例6 G a N係以等同於第一實例的方式成長至4微米之厚 度。利用電子束蒸鍍法將鎢（W)膜以2 0 nm之厚度 澱積於此基底晶體上。此樣品在氫.氣壓中及4 0 0 °C下保 持1 0分鐘，然後在氫氣及氨氣之混合氣壓中及6 0 0°C 下保持5分鐘，再將氫氣及氨氣之混合氣壓中的溫度升高 至9 5 0 °C。然後將樣品立即冷卻。X -射線光電子光譜 分析顯示氮化鎢係均勻地形成於鶴層中。由是製得的遮蔽 材料係具有圖樣並且再成長係以等同於第一實例的方式實 施。良好的內埋結構係如第一實例中者形成。對用於熱處 理之包括氨的氣壓而言，除了使用於實例中之氨氣與氫氣 的混合氣之外，其亦可以是氨氣與惰性氣體的混合氣。 (請先間讀背面之注意事項再填寫本頁) 訂---------線· 經濟部智慧財產局員工消費合作社印製 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -18-Ga (C2H5) 2C1) 'dimethyl indium chloride (I n (C Η 3) 2 C 1), diethyl indium chloride (I n (C 2 Η 5) 2 C 1), or the like Decomposed at high temperature to produce GaCl and InCl. It is also feasible to supply carrier gas bubbles to, for example, GaCi2, I nC 丨 2 (which appears stable at normal temperature). They can be used alone or in combination. Group V materials include, for example, ammonium, hydrazine, methylphenanthrene, 1,1-dimethyldimethylhydrazine, 1,2-dimethylhydrazine, tertiary butylamine, and ethylenediamine. These materials are used alone or in combination. Among these materials, the ammonium and hydrazine paper ruler (CNS) A4 specifications (210 X 297 mm) -13- ------! --------- i- -1--1 1 Order ·!-(Please read the note on the back? Matters before filling out this page) 472299 Γ Α7 ___— Β7 V. Description of the buckle) Advantages Because these elements do not contain carbon atoms, they can be made Carbon contamination of semiconductors is minimized 'and ammonium is better because it is easier to handle. (Please read the precautions on the back before filling out this page) S i, G e, or 0 is used as the η -type dopant for compound semiconductors. Among these dopants, s i is preferable because it is easy to produce a low-resistance η-type material and also because a high-purity raw material can be obtained. Raw materials that can be used for Si doping include, for example, SiHsCl and SiH2Cl2. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs In the present invention, sometimes the phenomenon of dents formed in the surface of the first V-V semiconductor layer after re-growth may occur, its manufacturing conditions and re-growth conditions It depends. As the first m-v compound semiconductor, a II-V compound semiconductor represented by the general formula I nuGavAlwN (〇 ^ u < l > 0 ^ v < 1, 〇 < wSI, u + v + w = 1) is used. The formation of this depression can sometimes be suppressed. In specific conditions, the A 1 N composition ratio (値 of w in the above general formula) is 1% or more, and more preferably 5% or more. Under specific conditions, the thickness of the first V-compound semiconductor layer is 0.3 nm or more, and preferably 1 nm or more. In general, the effect of suppressing the formation of depressions during re-growth will increase with the increase in the A 1 N composition ratio or the thickness of the first ID-V compound semiconductor layer, but at the same time, the The crystallinity tends to decrease; therefore, the thickness of the first m-V compound semiconductor layer must be adjusted according to the A 1 N composition ratio. Examples Example 1, Comparative Examples 1 -14-This paper size applies to the Chinese National Standard (CNS) A4 (210 X 297 mm) 472299 A7 B7 V. Description of the invention (12) (Please read the notes on the back before filling in this Page) First, a base crystal was prepared in the following manner. Using the M 0 v PE method, a buffer layer of G a N was grown on a sapphire substrate at a thickness of 50 nm at 5 50 ° C, and G a N was further advanced at about 1 100 ° C. Grow to a thickness of 4 microns. Then, W was deposited on the substrate crystal by sputtering to a thickness of 30 nm, and a stripe pattern having a 5-micron opening and a 5-micron stripe was formed by a conventional photolithography method. The direction of the stripes is the < 1-1 0 0 > direction. Then, using this crystal, it was further grown to a thickness of 33 µm by the ΗV P E method. In addition, S i 0 2 was used instead of W to form the pattern and used as the first comparative example, and the re-growth system was implemented in the same manner. In either case, the crystal produced by re-growth has a mirror-like surface. In order to examine the variation in orientation of the crystals obtained from the crystal, the X-ray swing curve was measured in a direction parallel to and perpendicular to the direction of the stripes. Figure 2 A and printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 2 B show the results. When the re-growth is implemented on the W pattern, the full width at the maximum half of the wobble curve is constant at 200 seconds or less, regardless of the direction of X-ray incidence, and no variation is observed in the crystal orientation. On the other hand, when it is a S i 0 2 pattern (comparative example), the full width at the maximum 値 half of the swing curve parallel to the direction of the pattern stripes is narrow, but at the maximum 値 half of the direction perpendicular to the stripes The full width of the image is increased to 750 seconds or more (see Figure 2B). This means that the crystal re-growth on the pattern has a variation in crystal orientation relative to the base crystal, and its crystallinity is insufficient compared to the case of the W pattern. The sample prepared in the first example was cleaved in a direction perpendicular to the pattern, and its cross-sectional area was observed under a transmission electron microscope to confirm the re-growth film> The paper size applies the Chinese National Standard (CNS) A4 specification. (Issued by X 297) Γ-Ι5-472299 A7 I ____-__ B7 V. Description of the invention (13) Not excessively grown on the W pattern. Example 2 (Please read the precautions on the back before filling this page) The G a a N film with reduced defects according to the present invention is formed by growing on a pattern with a striped pattern in the same manner as the first example. Appropriate layers are formed on the G a A 1 N film, and semiconductor processes (such as engraving and electrodeposition) are repeatedly performed to produce electronic devices such as HEMTs (high electron transport transistors) or feTs (electric field effect transistors). ). These electronic devices have excellent electrical properties and reliability because the number of crystal defects contained in the crystal as a function of the device can be reduced. Example 3 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs has a reduced The defective G a A 1 N film is formed on the pattern having the stripe pattern by being grown again in a manner equivalent to the first example. An η-type layer is formed on this G a A 1 N film, the layer having a band gap smaller than that of the η-type layer (light-emitting layer), and a P-type layer, each layer being formed of the compound semiconductor in the above order And semiconductor processes (such as etching and electrowinning) are repeatedly performed to produce light emitting devices such as light emitting diodes (LEDs) or semiconductor lasers (LDs). These light-emitting devices have excellent light-emitting characteristics and reliability, and extremely good life, because the number of crystal defects included in the crystal as a function of the device is reduced. Example 4 G a N is grown to a thickness of 4 microns in a manner equivalent to the first example. The paper size is applicable to the National Standard (CNS) A4 specification (2i0x 297 mm) 472299 A7 _______ B7 V. Description of the invention (14) Degree 'does not have GaA1N growing on it. The a1N composition ratio of this layer is about 15% 'and the thickness is 30 nm. A 20 to n m thick film of W was formed on this layer by an electron beam evaporation method, and a stripe pattern was formed by a conventional photolithography method. The stripe direction is the < 1 1 0 〇 > direction, and the stripe width and the stripe interval are both 5 m. Then, the growth was performed by the MV V PE method. The growth pressure is 40 kPa, and the thickness of the re-grown layer is 3 microns. The crystal obtained by further growth has a mirror-like surface. The samples prepared in the first and fourth examples were cleaved in a direction perpendicular to the fringe pattern and the cross-sectional area was observed under a transmission electron microscope; the results showed that although the base crystals of the samples prepared in the first example There is occasional damage phenomenon, but there is no damage phenomenon on the base crystal of the sample prepared in the fourth example. Example 5 G a N was grown to a thickness of 4 m in a manner equivalent to that of the first example. A Si 0 2 film is deposited on the substrate crystal by sputtering to a thickness of 50 to 70 nm, and a tungsten (W) film is deposited on the substrate crystal by sputtering to a thickness of 50 nm. Then, a stripe pattern was formed on each other using a conventional photo-imprinting technique. The stripe directions are the < 1-1 0 0 > and < 1 1-2 0 > directions. Then, re-growth was carried out by the low-pressure MOVPE method. The thickness of the regrown film was about 8 m. The sample prepared from the sample and the sample prepared in the first example were cleaved in a direction perpendicular to the fringe pattern, and the cross-sectional area was observed under a transmission electron microscope; the results showed that although the sample was observed on the sample of the first example The depression is formed under the mask, but it is made in the fifth example (please read the precautions on the back before filling in this page) • ------- Order --- ------ Line-Intellectual Property of the Ministry of Economic Affairs The paper size printed by the Bureau ’s Consumer Cooperatives applies the Chinese national standard (CNS > A4 size (210 x 297 mm) -17-472299 ---------- B7_______ V. Samples obtained from the invention description (15) On the other hand, it was found that the formation of depressions was greatly reduced. Example 6 G a N was grown to a thickness of 4 micrometers in a manner equivalent to the first example. The tungsten (W) film was formed to a thickness of 20 nm by the electron beam evaporation method. Deposited on the substrate crystal. The sample was held under hydrogen and pressure at 400 ° C for 10 minutes, and then kept under a mixed pressure of hydrogen and ammonia at 600 ° C for 5 minutes, and then The temperature in the mixed gas pressure of hydrogen and ammonia was raised to 950 ° C. Then the sample was immediately cooled. X-ray photoelectron spectroscopy analysis showed that the tungsten nitride system was uniformly formed in the crane layer. The shielding material system made from this had a pattern and the growth system was implemented in a manner equivalent to the first example. A good embedded structure system is as Formed in an example. For the gas pressure including ammonia used for heat treatment, in addition to the mixed gas of ammonia and hydrogen used in the example, it can also be a mixed gas of ammonia and inert gas. (Please first Note on the back of the occasional reading and then fill out this page) Order --------- Line · Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs, Consumer Cooperatives This paper is printed in accordance with China National Standard (CNS) A4 (210 X 297) Centimeters) -18-

Claims (1)

472299 A8 B8 C8 D8 --"It 六、申請專利範圍 附件A 第89 1 03 826號專利申請案 中文申請專利範圍修正本 民國90年7月修正 1 . 一種瓜一 V化合物半導體，其具有以通式 I n u G a v A 1 w N (其中 OSuSl ，〇 ^ v ^ 1 ，0 SwSl，u + v+ w=l)表示之第一個m — V化合物 半導體形成的層，由不同於該第一個瓜一V化合物半導體 且不同於下文中提及之第二個I[一V化合物半導體之材料 形成於該層上的圖樣，及以通式I η x G a y A 1 z N (其 中 OSxSl，OSySl，〇SzSl，x + y + z = 1 )表示之該第二個瓜一 V化合物半導體在該第一個ΙΠ V化合物半導體及該圖樣上形成的層，且其特徵爲不論X -光入射的方向爲何該第二個IE-V化合物半導體之（ 0 0 0 4 )反射X —光擺動曲線最大値一半處的全寬爲 7 0 0秒或以下。 (請先閱讀背面之注意事項再填寫本頁) 種]H — V化合物半導體，其具有以通式 (其中〇S u S 1 經濟部智慧財產局員工消費合作社印制衣 I riuGsvA lw ]M 1 u + v + 半導體形成的層，由不同於該第一個 且不同於下文中提及之第二個m—v 形成於該層上的圖樣，及以通式I η 中 OSxSl，OSySl，〇Sz 1 )表τκ之該第二個 V化合物半導體及該圖樣上形成的層，且其特徵爲該圖樣 0 W 1 )表示之第一個π — V化合物 皿一V化合物半導體 化合物半導體之材料 xGayAlzN (其 ^ 1 ，X + y + z = v化合物半導體在該第一個m— 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐）472299 A8 B8 C8 D8-" It VI. Application for Patent Scope Annex A No. 89 1 03 826 Patent Application Chinese Application for Patent Scope Amendment July 1990 Revision 1. A melon-V compound semiconductor with The first m — V compound semiconductor layer formed by the general formula I nu G av A 1 w N (where OSuSl, 〇 ^ v ^ 1, 0 SwSl, u + v + w = 1) is different from the first A pattern of a compound semiconductor that is different from the second I mentioned below. [The pattern of a compound semiconductor material formed on this layer, and the general formula I η x G ay A 1 z N (where OSxSl, OSySl, 〇zzSl, x + y + z = 1) represents the layer formed by the second melon-V compound semiconductor on the first III-V compound semiconductor and the pattern, and is characterized by the X-ray incident Why is the direction of the (0 0 0 4) reflected X-ray swing of the second IE-V compound semiconductor the full width at the maximum 値 half of the second IE-V compound semiconductor is 700 seconds or less. (Please read the precautions on the back before filling out this page) Kind] H — V compound semiconductor, which has the general formula (in which 0 S u S 1 printed by the Intellectual Property Bureau employee consumer cooperative of the Ministry of Economic Affairs I riuGsvA lw] M 1 A layer formed by u + v + semiconductor, a pattern formed on the layer different from the first and different from the second m-v mentioned below, and OSxSl, OSySl, in the general formula I η. Sz 1) The second V compound semiconductor of Table τκ and the layer formed on the pattern, and is characterized by the first π-V compound plate-V compound semiconductor compound semiconductor material xGayAlzN represented by the pattern 0 W 1) (Its ^ 1, X + y + z = v compound semiconductor in the first m — this paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 472299 A8 B8 C8 D8 六、申請專利範圍 的上表面不與該第二個m—v化合物半導體接觸。 3 .如申請專利範圍第1或2項之瓜一 v化合物半導 體，其中，該圖樣係由w形成。 4 .如申請專利範圍第1或2項之瓜一 v化合物半導 體，其中，第一個m — v化合物半導體係以通式 InuGavAlwN (其中 1，Ο . OlSwSl，u + v+ w==l)表不。 5 .如申請專利範圍第1或2項之Π[ — V化合物半導 體，其中，該圖樣係包含至少兩個彼此接觸且由不同材料 製成之層的層合物。 6 .如申請專利範圍第5項之瓜一 V化合物半導體， 其中，該圖樣係包含至少一個由W製成之層及一個由W之 外的材料製成之層的層合物。 7 .如申請專利範圍第5項之ΙΠ — V化合物半導體， 其中，該圖樣係包含至少一個由W製成之層及一個由 S i 〇2製成之層的層合物。 8 . —種電子裝置，其特徵在於其含有申請專利範圍 第1或2項之瓜一V化合物半導體。 經濟部智慧財產局員工消費合作社印製 9 . 一種發光裝置，其特徵在於其含有申請專利範圍 第1或2項之瓜一V化合物半導體。 -2 - (請先閱讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐〉472299 A8 B8 C8 D8 6. The upper surface of the scope of patent application is not in contact with the second m-v compound semiconductor. 3. The melon-v compound semiconductor according to item 1 or 2 of the patent application scope, wherein the pattern is formed by w. 4. The melon-v compound semiconductor according to item 1 or 2 of the patent application scope, wherein the first m-v compound semiconductor is represented by the general formula InuGavAlwN (wherein, 1.0. OlSwSl, u + v + w == l) Do not. 5. The Π [—V compound semiconductor according to item 1 or 2 of the patent application scope, wherein the pattern is a laminate comprising at least two layers that are in contact with each other and made of different materials. 6. The melon-V compound semiconductor according to item 5 of the scope of patent application, wherein the pattern comprises a laminate of at least one layer made of W and one layer made of a material other than W. 7. The compound Π-V compound semiconductor according to item 5 of the scope of patent application, wherein the pattern comprises a laminate of at least one layer made of W and one layer made of Si02. 8. An electronic device, characterized in that it contains a melon-V compound semiconductor in the scope of claims 1 or 2. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 9. A light-emitting device characterized in that it contains a melon-V compound semiconductor with the scope of patent application No. 1 or 2. -2-(Please read the notes on the back before filling out this page) This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm)
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