TW201234645A - Template, method for manufacturing the template and method for manufacturing vertical type nitride-based semiconductor light emitting device using the template - Google Patents
Template, method for manufacturing the template and method for manufacturing vertical type nitride-based semiconductor light emitting device using the template Download PDFInfo
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- TW201234645A TW201234645A TW100125704A TW100125704A TW201234645A TW 201234645 A TW201234645 A TW 201234645A TW 100125704 A TW100125704 A TW 100125704A TW 100125704 A TW100125704 A TW 100125704A TW 201234645 A TW201234645 A TW 201234645A
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- 150000004767 nitrides Chemical class 0.000 title claims abstract description 221
- 238000000034 method Methods 0.000 title claims abstract description 69
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 27
- 239000004065 semiconductor Substances 0.000 title claims abstract description 17
- 239000000758 substrate Substances 0.000 claims abstract description 57
- 238000005530 etching Methods 0.000 claims abstract description 21
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 4
- 230000008569 process Effects 0.000 claims description 52
- 238000002248 hydride vapour-phase epitaxy Methods 0.000 claims description 24
- 229910052751 metal Inorganic materials 0.000 claims description 17
- 239000002184 metal Substances 0.000 claims description 17
- 238000005229 chemical vapour deposition Methods 0.000 claims description 16
- 239000011800 void material Substances 0.000 claims description 13
- 238000001816 cooling Methods 0.000 claims description 7
- 239000012808 vapor phase Substances 0.000 claims description 3
- 238000000151 deposition Methods 0.000 claims description 2
- 239000004744 fabric Substances 0.000 claims 1
- BIXHRBFZLLFBFL-UHFFFAOYSA-N germanium nitride Chemical compound N#[Ge]N([Ge]#N)[Ge]#N BIXHRBFZLLFBFL-UHFFFAOYSA-N 0.000 claims 1
- 239000007943 implant Substances 0.000 claims 1
- 230000001678 irradiating effect Effects 0.000 claims 1
- 238000002488 metal-organic chemical vapour deposition Methods 0.000 claims 1
- 230000007547 defect Effects 0.000 abstract description 2
- 239000010410 layer Substances 0.000 description 193
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 25
- 239000007789 gas Substances 0.000 description 25
- 239000002086 nanomaterial Substances 0.000 description 13
- 239000000463 material Substances 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 11
- JMASRVWKEDWRBT-UHFFFAOYSA-N Gallium nitride Chemical compound [Ga]#N JMASRVWKEDWRBT-UHFFFAOYSA-N 0.000 description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 9
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 9
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 9
- 229910052594 sapphire Inorganic materials 0.000 description 8
- 239000010980 sapphire Substances 0.000 description 8
- 229910021529 ammonia Inorganic materials 0.000 description 7
- 229910002601 GaN Inorganic materials 0.000 description 6
- 229910052733 gallium Inorganic materials 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 5
- 238000001451 molecular beam epitaxy Methods 0.000 description 4
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 4
- 239000013078 crystal Substances 0.000 description 3
- 238000002309 gasification Methods 0.000 description 3
- 238000004626 scanning electron microscopy Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XCZXGTMEAKBVPV-UHFFFAOYSA-N trimethylgallium Chemical compound C[Ga](C)C XCZXGTMEAKBVPV-UHFFFAOYSA-N 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000012159 carrier gas Substances 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 239000008267 milk Substances 0.000 description 2
- 210000004080 milk Anatomy 0.000 description 2
- 235000013336 milk Nutrition 0.000 description 2
- 238000003892 spreading Methods 0.000 description 2
- 230000007480 spreading Effects 0.000 description 2
- PYRKKGOKRMZEIT-UHFFFAOYSA-N 2-[6-(2-cyclopropylethoxy)-9-(2-hydroxy-2-methylpropyl)-1h-phenanthro[9,10-d]imidazol-2-yl]-5-fluorobenzene-1,3-dicarbonitrile Chemical compound C1=C2C3=CC(CC(C)(O)C)=CC=C3C=3NC(C=4C(=CC(F)=CC=4C#N)C#N)=NC=3C2=CC=C1OCCC1CC1 PYRKKGOKRMZEIT-UHFFFAOYSA-N 0.000 description 1
- 241000239290 Araneae Species 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- 235000012766 Cannabis sativa ssp. sativa var. sativa Nutrition 0.000 description 1
- 235000012765 Cannabis sativa ssp. sativa var. spontanea Nutrition 0.000 description 1
- 101100136092 Drosophila melanogaster peng gene Proteins 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 208000012868 Overgrowth Diseases 0.000 description 1
- 206010036790 Productive cough Diseases 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- -1 bismuth nitride Chemical class 0.000 description 1
- 235000009120 camo Nutrition 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 235000005607 chanvre indien Nutrition 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- XOYLJNJLGBYDTH-UHFFFAOYSA-M chlorogallium Chemical compound [Ga]Cl XOYLJNJLGBYDTH-UHFFFAOYSA-M 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- AXTYOFUMVKNMLR-UHFFFAOYSA-N dioxobismuth Chemical group O=[Bi]=O AXTYOFUMVKNMLR-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- UPWPDUACHOATKO-UHFFFAOYSA-K gallium trichloride Chemical compound Cl[Ga](Cl)Cl UPWPDUACHOATKO-UHFFFAOYSA-K 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000011487 hemp Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- NFFIWVVINABMKP-UHFFFAOYSA-N methylidynetantalum Chemical compound [Ta]#C NFFIWVVINABMKP-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000000206 photolithography Methods 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000001902 propagating effect Effects 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 239000012465 retentate Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 210000003802 sputum Anatomy 0.000 description 1
- 208000024794 sputum Diseases 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 229910003468 tantalcarbide Inorganic materials 0.000 description 1
- 238000000927 vapour-phase epitaxy Methods 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
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- 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
- H01L21/02436—Intermediate layers between substrates and deposited layers
- H01L21/02439—Materials
- H01L21/02455—Group 13/15 materials
- H01L21/02458—Nitrides
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- H01L33/02—Semiconductor devices having potential barriers 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
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- H01L21/02365—Forming inorganic semiconducting materials on a substrate
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Description
201234645 六、發明說明: 【發明所屬之技術領域】 本發明係關於一種利用模板製造氮化物基半導體發光器件之 技術。 【先前技術】 由於氮化物基半導體發光n件具有壽命長、功耗低、初始驅 動特性極好、抗振性強等多種優點,因此對其f求與日俱增。 -般而言,氮化物基半導體發絲件包含有多錢化物層, 攻些氮化物層包含有-n型氮化物層、—活性層以及型氮化 物層。其中,η型及ρ型氮化物層為活性層提供電子及電洞,從而 透過電子與電洞在此活性層巾之再結合發出光線。 *然而’諸如藍寶石(剔3)等材料製成的基底之晶格常數通 常與氮化物層的;F相同,因此#在基底上直接生長氮化物層時會 發生嚴重之晶格畸變,此,近年來提出—種減少氮化物層生長 過程中晶格畸變之方法,此方法_ 了—種具有沉積於基底上的 未摻雜氮化物叙她。細,較细此種方法,錯位密度仍 然為酬lGH)/em2 ’所以其騎善氮化物層晶體品質 限。 π 立最近’已經提出了一種生長技術,用以減少錯位密度,例如 (epitaxial lateral overgrowth, ELO) 〇 -儿積有未摻雜氮化物層的模板上形成具有圖案的二氧 201234645 化石夕(Si02)掩模’然後自掩模的開口生長氣化物層,從而弓丨起 掩模上之橫向生長。然而,由於此生長技術包含有基於化學氣相 讀(CVD)的二氧化石夕(Si〇2)獏沉積、塗光刻膠、光刻、姓 刻以及清洗等步驟,因此製造過程繁瑣,花費時間很多。 【發明内容】 因此’繁於上述問題,本發明的一個方面在於提供一種模板 之製造方法以及-種棚該模板製造氮化物基半導體發光器件的 方法’其巾在基底上職具有纽結構之氮化倾衝層,從而減 少由於基底與氮化物層晶格常數之差異造成的應力,同時防止錯 位之發生。 根據本發明的-個方面’―種模板之製造方法包含:在基底 上生長-第-氮化物層;透過向第—氮化物層之頂面供給氯化物 絲刻氣體’以侧第—纽物層之頂面;透過在第—氮化物層 之頂面上生長-第二氮化物層’以形成多個第—空隙;透過向第 二氮化物層之頂面供給此_氣體以_第二氮化物層之頂面; 以及透過在第:氮化物層之頂面上生長—第三氮化物層,以形成 多個第二空隙。 、,根據本&明之方面,—種製造垂直型氮化物基半導體發 =器件的方法包含:透過多次重触長氮化物層之過程及蚀刻過 私’在-生長基底上生長—具有多個空隙之氮化物緩衝層 ;在氮 化物緩衝層的頂部上生長1型氮化物層、—活性層以及一p型 201234645 氮化物層;在!>魏化物層之頂部上形成一導電基底;利用形成 这些空隙的部份作為蝴表面去除生長基底;以及透過處理切割 表面用以形成一電極極板。 【實施方式】 以下將參照附圖具體描述本發明之示例性實施例。在以下之 實施例中’ ^要描述驗製造發光科之觀。細,本發明並 不限於此’但可以應用於用以生長氮化物層的各種模板。 應該理解的是,當諸如層、膜、區域絲底的-個元件被稱 作位於另-元件“之上”時’可以為該耕直接位於另一元件之 上,也可以存在插入之元件。相反,當一個元件稱作“直接,,位 於另-元件“之上,,時,财存在插人之元件。 「第1圖」是根據本發明示例性實施例之模板10之剖視圖。 如「第1圖」所示’根據本實施例之模板10包含有一基底1〇〇, 以及一在基底100上生長的氮化物緩衝層2〇〇。氮化物緩衝層2⑻ 具有多孔結構,該多孔結構中形成有多個空隙213、223,並且在 氮化物緩_ 200上可財長輯疊其⑽氮化物層。 基底100限定了一個基面,氮化物層開始在其上生長。該基 底100係由適合氮化物層的晶格生長之材料製成。在本實施例之 中’將藍寶石(Α1203)基底用作基底励。這裏,藍寶石基底具 有/、角形結構,並且在高溫下穩定。此外,可以使用由例如尖 晶石(MgAi04)、碳化矽(Sic)、矽(幻)、氧化鋅(Ζη〇)、砷化 201234645 鎵(AsGa)或者氮化鎵(⑽)等材料製成的基底。 在藍寶石基底觸上形成氮化物緩衝層·
少观乳1匕物緩衝層2〇〇。在本實施例中, 樣具有六角系結構的氮化鎵(GaN)層 象者,可以利用第ΠΙ族氮化物層構建氮 ,鼠化物緩衝層200形成為堆疊有乡個由氮化鎵(GaN)材料 製成的氮化物層之結構。氮化物緩衝層·係為在藍寶石基底卿 上生長氮錄料,透触職化物層之—的麻,繼而在氮化
在本實施例中,氮化物緩衝層包含有—第—氮化物層 21〇、-第二氮化物層22(Ux及-第三氮化物層23G。多個第一空 隙213形成於鄰近第-氮化物層21〇與第二氮化物層22〇之間的 介面之部份處’多個第二空隙形成於鄰近第二氣化物層22〇與第 三氮化物層230之間的介面之部份處。 因此’如「第1圖」所示,在第一空隙213之頂部上形成第 二空隙223,從而可以形成在其中多個空隙排列為兩層結構之結 構。而且,第二空隙223與先前形成的第一空隙213在部份位置 組合在一起’從而可以形成大尺寸的空隙結構。 「第2圖」係為製造「第1圖」之模板過程之流程圖,「第3 201234645 。下文中,將 緩衝層200的 圖」係為說明「第2圖」之模板製造過程之剖面圖 參閱「第2圖」及「第3圖」詳細描述生長氮化物 方法。 如「第3 U)圖」所示,在步驟S1〇之中,第—氮化物層21〇 在藍寶石基底_上生長為0.2至1G微米(μη〇厚。該作業可以 利用金射機化學氣相沉積(M〇CVD)裝置、魏物氣相外延 (Hydride Vapor Phase Epitaxy,HVPE)裝置或者分子束外延 (MolecularBeamEpitaxy,MBE)裝置來完成。在本實施例中採 用金屬有機化學氣相沉積(MOCVD)裝置,以確佩化物層的晶 格能夠令人滿意地生長。 在本實施例中,將藍寶石基底100放置於金屬有機化學氣相 沉積(MOCVD )裝置之内’並將三甲基鎵(TMGa)及氨氣(細) 連同作為載氣的氫氣(H2)-起供給至金屬有機化學氣相沉積 (MOCVD )裝置中’由此生長出由未摻雜氮化嫁(GaN ) ( u_GaN ) 材料製成的第一氮化物層210。在此生長過程的初始階段,透過在 500至700 C的低溫下保持大約10至30分鐘,生長2〇奈米(啦) u-GaN層’用以形成緩衝層,然後透過升溫至⑻至丨2〇〇。〇,將 未摻雜氮化鎵(GaN)(u-GaN)層又生長至大約2微米(μιη)厚。 第一氣化物層由此形成。 在生長第一氮化物層210之後,將基底1〇〇自金屬有機化學 氣相沉積(MOCVD)裝置轉移至氫化物氣相外延(HVPE)裝置, 201234645 氫化物氣相外延(HVPE)裝置之内部溫度升高至800°c或更高。 然後’在步驟S20之中,透過將氣化物基氣體及氨氣(NH3)供 ' 給至氩化物氣相外延(HVPE)裝置中以進行初級蝕刻過程。在本 實施例中’將氯化氫(HC1)用作氯化物基氣體的一個實例。這裏, 即使在僅供給氣化氫(HC1)或僅供給氨氣(ΝΉ3)時,也能夠獲 得钮刻第一氮化物層之效果。然而,該氮化物層未被姓刻處的結 構會變得不穩定。因此,可以1〇〇〇sccm或更小的速率將氣化氫 (HC1)氣與以1〇〇至2〇〇〇 sccm的速率將氨氣(胃3)供給至氫 化物氣相外延(HVPE)裝置中。在本實施例中,透過以3〇〇sccm 的速率供給氣化虱(HC1)氣並且以1〇〇〇5(^111的速率供給氛氣 (NH3)來進行钱刻。 第4圖」係為在前述過程條件下,初級敍刻過程進行了 μ 分鐘之後的第一氮化物層頂面之掃描式電子顯微鏡(SEM )照片。 如「第4圖」所示’隨著透過第一侧過程在第一氮化物層21〇 之頂面上向下進行各向異性侧,在第—氮化物層2ig被充分進 行钕刻的位置形成了多個第一低谷結構212,而在第一氮化物層 210未充分進行_的位置形成多個柱狀的第—納米結構2ΐι。 透過健氯化氫(HC1)氣與氨氣⑽3)之混合比及供給量 似進行_㈣間,可蛛纖_程帽朗姆結構及低 夺結構之尺寸及職。此蝴触可以進行5至%分鐘。 透過初級餘刻過程在第一氮化物層21〇的頂部上形成了多個 201234645 第一納米結構211及多個第一低谷結構212之後,在第一氮化物 層210的頂部上生長第二氮化物層22〇(S3〇)。可以利用金屬有機 化學氣相沉積(MOCVD)裝置、氫化物氣相外延(HVpE)裝置、 分子束外延(MBE)裝置等進行第二氮化物層22〇之生長。在本 實施例中,利用氫化物氣相外延(HWE)裝置生長第二氮化物層 220。此種情況下,透過將生長第二氮化物層22〇的過程連同初級 姓刻過程以及It後的次級侧過程…起就地在氫化物氣相外延 (HVPE)裝置中進行’能夠簡化製造過程。 在完成初級餘刻過程之後,將金屬有機化學氣相沉積 (MOCVD)裝置内部的溫度升高至1〇〇〇至13〇〇t>c,然後將氯化 鎵(GaCl) 及氨氣(聰)供給至金屬有機化學氣相沉積 (MOCVD)裝㈣擁使得氯化氫⑽)氣經過包含有 鎵源的鎵舟’通過氣化氫(HC1)氣與鎵的反應生成氣化錄(Gaa) 氣。 在這個過程中,在第一敗化物層210的頂部上,透過氣化鎵 (GaCl)氣與氨(NH3)氣的之_反應形成了由氮化鎵(祕) 材料製成的第二氮化物層22〇。如「第3 (〇圖」所示,在第一 納米結構2Π的頂部上生長一第二氮化物層22〇,同時形成屋頂結 構’並且與第-低谷結構212及第一納米結構211 —起形成多個 第一空隙213。 同時,在完成第二氮化物層22Q之生長之後,在第二氮化物 201234645 層220上進行次級蝕刻過程(S40)。如上所述,次級蝕刻過程係 在氫化物氣相外延(HVPE)裝置中就地進行的。在次級蝕刻過程 之中,與初級钮刻過程一樣,在氫化物氣相外延(pjypE)裝置的 内部溫度保持在80(TC或更高的狀態下,將氯化物基氣體(本實施 例中採用氣化氫氣體)及氨(NH3)氣供給至氫化物氣相外延 (HVPE)裝置中。隨著各向異性侧之進行,在第二氮化物層 220頂面進一步被钮刻的位置形成了向下凹陷形狀之多個第二低 谷結構222,並且在第二氮化物層220頂面未被進一步姓刻的位置 形成柱狀的多個第二納米結構221。 如「第3⑷圖」所示,在相對弱地進行第二侧過程的位 置,進行各向異性蝕刻所達到之深度相比較於在第一空隙上方形 成屋頂的第二氮化物層之厚度域(參見區域〇,因此,第二低 合結構222及第二納米結構221可形成於第一空隙213的頂部上。 隨著在第-_ 213之頂部上形成屋頂的第二氮化物層22〇 被钱刻’在娜強地進行:欠級侧過程的健,先前形成的第一 空隙犯向上打開(參見區域B)。因此,在該位置,次紐刻過 程中形成的第二低谷結構222能夠形成為具有相對大的寬度及深 度,同時包含有先前形成的第一空隙213之區域。 如上所述’在形成第一空隙213之情況下進行次級侧過程, 並且由此可以根據進行钱刻之程度以形成不同的結構。因此,透 過控制第二氮化物層220之生長厚度、進行次級侧過程的持續 201234645 時間以及次級蝕刻過程中蝕刻氣體之流速等,能夠形成形狀各異 的結構。 在次級蝕刻過程完成之後,進行冷卻基底1〇〇預定時間之作 業。在氳化物氣相外延(HVPE)褒置中透過自然冷卻,以進行該 冷卻作業,並且透過此過程能夠穩定基底上生長的氮化物層。該 冷卻作業可_行I5至60 。在本實關之巾,自然冷卻進 行30分鐘。 隨後’將基底100自氫化物氣相外延(HVPE)裝置轉移至金 屬有機化學氣才積(MOCVD )袭置,以生長第三氮化物層23〇。 可以在除金屬有機化學氣相沉積(M〇CVD)裝置之外的裝置中生 長第二氮化物層230。然而,在本實施例中,第三氮化物層23〇 形成氮化物緩衝層200之上部結構,因此採用金屬有機化學氣相 沉積(MOCVD)裝置可獲得令人滿意之晶格生長。 首先將基底1〇〇放置於金屬有機化學氣相沉積(M〇CVD)裝 置之内’絲透過驅動加熱H以升高過程空間的溫度,從而形成 第三氮化物層230之生長環境。可以將氨(NH3)氣連續地供給 至金屬有機化學氣相_ (M〇CVD)裝置,同時升高過程空間的 ’皿度。如上所述,由於氨(細)氣供給至金屬有機化學氣相沉 積(MOCVD)裝置,因此可以防止溫度升高過程中先前生長的第 一氮化物層210與第二氮化物層22〇產生裂紋,並且可以去除基 底1〇〇之轉移作業中在第二氮化物層220上形成的氧化物膜。 201234645 如果金屬有機化學氣相沉積(M〇CVD)裳置的溫度得到充分 之升高,則透過將三f基鎵(TMGa)及氨(鹏)氣連同作為載 氣的氫氣(H2) 1供給至金屬有機化學氣相沉積⑽㈣) 裝置中’生長由氮化鎵(⑽)材料製成的第三氮化物層23〇。 在該過程之初始階段,與一般的氮化鎵(GaN)生長環境相 比較’可⑽餘對健及高溫之環境,由此可以在第二氛化物 層220之納米結構221的上部進行水準生長。因此,在本實施例 中,在1150至125CTC的高溫以及2〇〇 mb或更低的低壓環境下, 透過自第二納米結構22i的頂部上沿著水準方向生長第三氮化物 層230以形成屋頂結構。透過將過程環境控制為溫度在麵至 120CTC、壓強在300mb或更大,使得氮化鎵(㈣層)垂直生長 至大約1至5微米(μιη)。氮化物緩衝| 之上部結構由此形成。 如「第3(e)圖」所示,透過該過程,第三氮化物層23〇連 同第二納米結構221及第二低谷結構222 一起形成多個第二空隙 223。依照透過次紐刻過程形成的第二低谷結構222,可以形成 多種形狀之第二空隙223。 第二空隙223形成於第-空隙213上部形成第二低谷結構的 位置處之第-空隙213的上方(參見區域〇。即,鄰近第一氮化 物層2Η)#第二氮化物層22G<間的介面形成第一郎:213,並且 鄰近第二氮化物層220與第三氮化物層23()之間的介面形成第二 空隙223,由此形成空隙以兩層排列之結構。 201234645 另方面,在第二低谷結構延伸至先前形成有第一空隙扣 的空間之位置處’第二空隙223形成為與先前形成第一空隙抝 的區域組合在一起(參見區域B)。因此’如「第3(e)圖」所干, 與未與第一空隙213組合在一起的其他空隙213相比,上述形成 的第二空隙223形成為更大之尺寸。 第5圖」係為由「第2圖」的方法製造的氛化物緩衝層之 橫截面之掃描式電子顯微鏡(SEM)照片。如「第5圖」所^, 透過多次進行生長氮化物層的過程以及_氮化物層的過程,氣 化物緩衝層勘中可以形成有不同結構之« 213及223。 空隙的結構可以減少由於氮化物層與藍寶石基底之間晶格常 數及熱膨脹的不同而造成之應力。而且,由於^_結構消除了 4近基底100的氮化物層中產生之錯位,由此可以防止錯位蔓延 至氮化物層的上部。特別地,在多個空隙佈置為堆疊排列之結構 中,上部的空隙防止一些錯位經過下部空隙蔓延,由此加倍阻止 了錯位之蔓延。 實際上,通過測量根據本實施例所生長的氮化物緩衝層所獲 知之結果為,即使在氮化物緩衝層為2至4微米(μιη)厚時,所 測得的錯位為大約l〇6/Cm2,這表明,與常規氮化物緩衝層相比, 氮化物緩衝層之錯位密度降低了 1%或更多。 因此’根據本發明實施例之模板具有其中的應力減少並且錯 位密度降低的氮化物緩衝層,從而可以生長出氮化物緩衝層頂面 14 201234645 之晶體品質令人滿意的發絲魏化騎,以及製造出實驗结果 表明與常規發光器件相比較,發光效率提高了 30至·的發光器 件。 同時,在前面之實施例中,已經描述了包含空隙佈置為堆疊 排列於-佩化物緩衝射的結構,奴具妓尺核隙的結構 之配置。然而,這僅僅係為便於說明而糾之實例,本發明並不 限於此。也就是說,透驗_二統物狀生長厚度、進行次 級侧過程之制咖、蝴氣體之流速等,可鄉成各種結構 的空隙。在本實施例中,姓刻過程進行了兩次。然而,侧過程 與生長鼠化物層的過程可以重複進行三次或更多次。 在根據本發明實施例之模板中,如上所述可以在氮化物緩衝 層的頂面上生長發光器件之氮化物層。「第6圖」係為利用根據本 發明示例性實施例之模板的橫向型氮化物基半導體之剖視圖。 如「第6圖」所示,垂直的氮化物基半導體發光器件2〇的結 構係為一 η型氮化物層310、一活性層32〇以及一 p型氮化物層 330順序地堆疊於模板1〇上。因此,在金屬有機化學氣相沉積 (MOCVD)裝置中生長氮化物緩衝層20〇之第三氮化物層23〇, 並且可以透過連續的過程生長發光器件的氮化物層。 在如本實施例中所述的利用未摻雜氮化鎵(GaN)材料生長 第一氮化物層210、第二氮化物層220以及第三氮化物層230的情 況下,透過控制溫度及過程氣體以生長第三氮化物層230並且順 201234645 序地生長η型氮化物層310、活性層320以及p型氮化物層330。 或者’在進行次級蝕刻過程之後’可以生長η型氮化物層作 為第二氮化物層230 ’然後可以在η型氮化物層上額外地生長活性 層以及ρ型氮化物層。 如上所述,在根據本實施例的橫向型氮化物基半導體發光器 件20中’在鄰近基底1〇〇之氮化物層中形成多個空隙214,由此 降低了氮化物層之應力及錯位密度。因此,可以改善内部量子效 率以及防止極化。 空隙具有與相鄰的氮化物層不相同之折射率。因此,朝向基 底傳播的光線在經過多個空隙時被散射或折射,使得光路改變。 由此可以改善發光器件之光提取效率。 同時,根據本發明實施例的模板還可以應用於垂直的氮化物 基半導體發光器件。「第7圖」示意性地表示利用根據本發明示例 性貫施例之模板製造垂直的氮化物基發光器件3〇〇的方法。 與上述的模板之製造方法相似,透過重複地生長氮化物層之 過程以及蝕刻氮化物層之過程,在生長基底上生長具有多孔結構 的氮化物緩衝層200。然後,直接在蝕刻過程所形成的納米結構之 上部生長η型氮化物層410、活性層420以及ρ型氮化物層430。 此氮化物緩衝層係為第三氮化物層,並且可以在氮化物緩衝層的 頂部上生長η型氮化物層。在未摻雜氮化物層與11型氮化物層之 間的邊界處佈置多個空隙(參見「第7 圖」)。 201234645 在多層氮化物層的生長完成之後,在P型氮化物層430之頂 部上形成一導電粘結層44〇,並且將導電基底45〇附著至導電粘結 層440。這裏,導電基底45〇與外部電路電連接,從而形成一 p 側電極。 接著,進行自氮化物層上去除生長基底1〇〇之作業(參見「第 7 (b)圖」)。由於氮化物緩衝層以納米結構之形式存在,因此其 中形成有夕個空隙213、223的區域與其他氮化物層相比較具有相 對弱的結構。因此,利用多個空隙213、223之形成位置作為表面 犧牲層’可以容易地將生長基底廳與氣化物層相分離。特別地, 在如模板之製造方法情述的透衫次進行_過卿成大尺寸 空隙的情況下’表面犧牲層之結構更弱,因此生長基底的分離可 以更容易地進行。 可以採用雷射剝離(laserlift_〇ff,LL〇)過程,透過使用雷射 照射鄰近生長基底100之氮化物層,用以去除基底。常規情況下, 由於氮化物層構成強晶格結構,因此在雷射照㈣氮化物層嚴重 受損,從而降低生產率。_,根據本發明,时射照射由於存 在多個空隙犯、奶而結構相對弱的位置,從而可以最小化對氣 化物層之損壞。 除上述雷射剝離0X0)過程之外,可以透過控制氮化私 及生長基底100的溫度’將絲基底⑽與氮化物層相分離。 為氣化物層與歸石製朗生絲底之間的鱗脹係數相差很 17 201234645 大,所以自氮化物層在生長基底上生長時的高溫開始進行冷卻, 使得在氮化物層中由於熱形變產生很大的應力。在試驗結果中, 隨著生長基底被冷卻’沿著形成這些空隙的部份產生裂紋,透過 向這些部份額外提供少量的能量便可將生長基底與氮化物層相分 離。 如上所述’在根據本發明實施例之發光器件中,基於形成多 個空隙的位置,可以谷易地將生長基底與氮化物層相分離。而且, 因為在分離生長基底時施加至氮化物層的應力變化相對小,所以 與常規發光器件相比較,可以形成品質令人滿意的自支撐層 (freestanding layer )。 同時,在分離生長基底100之後,進行處理表面犧牲層以暴 露η型氮化物層410之作業,用以形成電極極板46〇。常規上,難 以在決定處理表面犧牲層時決定是否暴露η型氮化物層41〇的同 時進行這個作業。然而,根據本發明,因為表面犧牲層形成於未 摻雜氮化物層與η型氮化物層410的邊界處,所以能夠容易地進 行該作業。 如上所述,可以形成品質令人滿意的氮化物層,並且提供了 一種製造更容易、發光效率及壽命優異之發光器件。 因此,根據各個實施例,透過未摻雜氮化物層中所形成的多 個空隙能夠減少晶格間應力及錯位缺陷,由此提高模板上額外生 長的氮化物層之品質。 201234645 而且,當利用該模板製造發光器件時,可以使得製造過程更 加容易,並且增強發光器件之發光效率。 儘管本文中描述了一些實施例,但本領域技術人員應當明 白丄這些實施例僅是為了 祕出’在不背離發明精神與範圍 的則提下可u進行各種修改、寵以及義。因此,本發明的範 圍僅應由專利申請範圍及其等價物來限定。 【圖式簡單說明】 第1圖係為根據本發明示例性實施例之模板之剖視圖; 第2圖係辅造第1圖之模板之過程之流程圖; 第3圖係為翻第2圖之模板製造過程之剖面圖; 化物二4 Γ糸為透過進行第3圖中的初級侧過程獲得的第-氮 :了、面之掃描式電子顯微鏡(SEM)照片,· (SE=)2料f 1 w之她的縣面之翻式電子顯微鏡 型氮本發明— 第7…發先器件之剖視圖;以及 型氮化物物糊罐㈣謎造的垂直 牛導體發光器件之剖視圖。 【主要元件符號說明】 10
模板 氮化物基半導體發光器件 19 201234645 100 基底 200 氮化物緩衝層 210 第一氮化物層 211 第一納米結構 212 第一低谷結構 213、214、223 空隙 220 第二氮化物層 221 第二納米結構 222 第二低谷結構 230 第三氮化物層 300 氮化物基發光器件 310 、 410 η型氮化物層 320 、 420 活性層 330 、 430 Ρ型氮化物層 440 導電點結層 450 導電基底 460 電極極板 20
Claims (1)
- 201234645 七、申請專利範圍: " 1. 一種模板’係包含有: • 一基底;以及 一氮化物_層’係軸於該絲以具有衫條線堆疊 及排列的多個空隙。 2. 一種模板之製造方法,係包含: 在基底上生長一第一氮化物層; 透過將氯化物絲刻氣體供給至該第一氮化物層之頂 面,用以蝕刻該第一氮化物層之頂面; 透過在該第-氮化物層之頂面上生長第二氮化物層,用以 形成多個第一空隙; 一透過將侧氣體供給至該第二氮化物層之頂面,用以餘刻 该第二氮化物層之頂面;以及 …透過在該第二氮化物層之頂面上生長—第三氮化物層,用 以形成多個第二空隙。 3. 第1 2項所述之模板之製造方法,其中在-金屬有機化 二目'儿積(MOCVD)裝置中生長該第一氮化物層以及該第 二氮化物層。 21 1 項所述之模板之製造方法,其中在-氮化物氣相 外延⑽DU裝置中生長該第二氮化物層。 2 5.如明未項第2項所糊板之製細,其中爾二空隙佈 201234645 置為堆疊排列於該等第一空隙之上。 6. 如請求項第5項所述之模板之製造方法,其中進行蝕刻該第二 氮化物層所達到之深度相比較於該第二氮化物層之厚度為淺。 7. 如請求項第5項所述之模板之製造方法,射鄰近該第一氮化 物層與該第二氮化物層之間的介面形成該等第—空隙,並且鄰 近該第二氮化物層與該第三氮化物層之間的介面形成該等第 二空隙。 &如請求項第2項所述之模板之製造方法,其中自該第二氮化物 層之頂面侧該第二氮化物層,以與該第一空隙相連通。 9. 如請求項第8項所述之模板之製造方法,其中該第二空隙相比 較於該第一空隙為大。 10. -種製造垂直型氮化物基半_發絲件的方法,係包含: 。透過重複兩次或更多次生長氮化物層之過程及餘刻過 私’在-生長基底上生長—具有多個空隙之氮化物緩衝層; 在該氮化物緩衝層的頂部上生長一 η型氮化物層、一活性 層以及一Ρ型氮化物層; 在該ρ型氮化物層之頂部上形成-導電基底; .利用形成該等空隙之部份作為切割表面,去除該生長基 底,以及 透過處理該切割表面形成-電極極板。 .如》月求項第10項所述之製造垂直型氮化物基半導體發光器件 22 201234645 的方法,其中生長該氮化物緩衝層係包含: 在該生長基底上生長一第一氮化物層; 透過將姓刻氣體供給至該第-氮化物層之頂面,以侧該 第一氮化物層的頂面; 透過在該第—氮化物層之頂面上生長-第二氮化物層以 形成多個第一空隙; 透過將該蝕刻氣體供給至該第二氮化物層之頂面,用以蝕 刻該第二氮化物層之頂面;以及 透過在該第二氮化物層之頂面上生長一第三氮化物層,用 以形成多彳固第二空隙。 如請柄第u顿述之製造垂直魏化祕半導體發光器件 的方法,其中在金屬有機化學氣相沉積(m〇cvd)裝置中生 長該第-氮化物層及該第三氮化物層,以及在氫化物氣相外延 (HVPE)裝置中生長該第二氮化物層。 13. 如請求項第10顿述之製造垂直魏化祕轉體發光器件 的方法,其中透過在該氮化物緩衝層中形成至少兩行,使得該 等空隙佈置為堆疊排列。 14. 如請求項第10項職之製造垂直魏化物基半導體發光器件 的方法,其中去除該生長基底包含用雷射照射其中形成有該等 空隙之部份。 15·如請求鮮10柄述之製造垂直魏化絲半導體發光器件 23 201234645 的方法,其中去除該生長基底包含冷卻該氮化物緩衝層,從而 在其中形成有該等空隙之部份產生裂紋。 16. -種垂直型氮化物基半導體發光器件,該半導體發光器件透過 以下方法製造: 透過重複兩-人或更多次生長氮化物層之過程及钮刻過 程,在-生長基底上生長—具有多個空_氮化物緩衝層; 在該氮化物緩衝層之頂部上生長一η型氮化物層、一活性 層以及一p型氮化物層; 在該P型氮化物層之頂部上形成—導電基底; 利用形成該等空隙之部份作為切#1表面,去除該生長基 底;以及 透過處理該切割表面形成一電極極板。
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JP2005085851A (ja) * | 2003-09-05 | 2005-03-31 | Hitachi Cable Ltd | 窒化物系化合物半導体発光素子の製造方法 |
KR100744933B1 (ko) * | 2003-10-13 | 2007-08-01 | 삼성전기주식회사 | 실리콘 기판 상에 형성된 질화물 반도체 및 그 제조 방법 |
US20060270201A1 (en) * | 2005-05-13 | 2006-11-30 | Chua Soo J | Nano-air-bridged lateral overgrowth of GaN semiconductor layer |
US20070138505A1 (en) * | 2005-12-12 | 2007-06-21 | Kyma Technologies, Inc. | Low defect group III nitride films useful for electronic and optoelectronic devices and methods for making the same |
JP5187610B2 (ja) * | 2006-03-29 | 2013-04-24 | スタンレー電気株式会社 | 窒化物半導体ウエハないし窒化物半導体装置及びその製造方法 |
JP5307975B2 (ja) * | 2006-04-21 | 2013-10-02 | 日立電線株式会社 | 窒化物系半導体自立基板及び窒化物系半導体発光デバイス用エピタキシャル基板 |
KR100818452B1 (ko) * | 2006-10-31 | 2008-04-01 | 삼성전기주식회사 | Ⅲ족 질화물 반도체 박막 제조방법 및 이를 이용한 질화물반도체 소자 제조방법 |
KR101004310B1 (ko) * | 2008-07-25 | 2010-12-28 | 고려대학교 산학협력단 | 광추출 효율이 향상된 발광 소자 및 그 제조 방법 |
US8247314B2 (en) * | 2008-11-14 | 2012-08-21 | Soitec | Methods for improving the quality of structures comprising semiconductor materials |
JP5313651B2 (ja) * | 2008-12-17 | 2013-10-09 | スタンレー電気株式会社 | 半導体素子の製造方法 |
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- 2011-06-22 JP JP2011138929A patent/JP2012142545A/ja not_active Withdrawn
- 2011-07-20 TW TW100125704A patent/TW201234645A/zh unknown
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WO2012093758A1 (ko) | 2012-07-12 |
EP2472566A2 (en) | 2012-07-04 |
JP2012142545A (ja) | 2012-07-26 |
EP2472566A3 (en) | 2013-04-17 |
US20120187444A1 (en) | 2012-07-26 |
KR20120079393A (ko) | 2012-07-12 |
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