TW201405725A - 用於半導體處理之玻璃－陶瓷基板 - Google Patents
用於半導體處理之玻璃－陶瓷基板 Download PDFInfo
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- 239000000758 substrate Substances 0.000 title claims abstract description 55
- 239000002241 glass-ceramic Substances 0.000 title claims abstract description 20
- 239000004065 semiconductor Substances 0.000 title claims abstract description 9
- 239000000463 material Substances 0.000 claims abstract description 18
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910002601 GaN Inorganic materials 0.000 claims description 26
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 14
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 12
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 10
- 239000011521 glass Substances 0.000 claims description 10
- 229910052737 gold Inorganic materials 0.000 claims description 4
- 229910052763 palladium Inorganic materials 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- 229910052709 silver Inorganic materials 0.000 claims description 4
- 229910000859 α-Fe Inorganic materials 0.000 claims description 3
- 229910000980 Aluminium gallium arsenide Inorganic materials 0.000 claims description 2
- 229910005540 GaP Inorganic materials 0.000 claims description 2
- 229910000530 Gallium indium arsenide Inorganic materials 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 229910052785 arsenic Inorganic materials 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 229910052733 gallium Inorganic materials 0.000 claims description 2
- 229910052738 indium Inorganic materials 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims 1
- 229910052661 anorthite Inorganic materials 0.000 abstract description 3
- 229910052634 enstatite Inorganic materials 0.000 abstract description 3
- 235000012215 calcium aluminium silicate Nutrition 0.000 abstract 1
- 229910052594 sapphire Inorganic materials 0.000 description 7
- 239000010980 sapphire Substances 0.000 description 7
- 239000013078 crystal Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 238000004630 atomic force microscopy Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- JMASRVWKEDWRBT-UHFFFAOYSA-N Gallium nitride Chemical compound [Ga]#N JMASRVWKEDWRBT-UHFFFAOYSA-N 0.000 description 3
- 238000005452 bending Methods 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
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- 244000225942 Viola tricolor Species 0.000 description 2
- 235000004031 Viola x wittrockiana Nutrition 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- GWWPLLOVYSCJIO-UHFFFAOYSA-N dialuminum;calcium;disilicate Chemical compound [Al+3].[Al+3].[Ca+2].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-] GWWPLLOVYSCJIO-UHFFFAOYSA-N 0.000 description 2
- 238000001493 electron microscopy Methods 0.000 description 2
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- 230000003746 surface roughness Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 1
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 description 1
- 229910052878 cordierite Inorganic materials 0.000 description 1
- 210000003298 dental enamel Anatomy 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 1
- 239000006112 glass ceramic composition Substances 0.000 description 1
- BBCCCLINBSELLX-UHFFFAOYSA-N magnesium;dihydroxy(oxo)silane Chemical compound [Mg+2].O[Si](O)=O BBCCCLINBSELLX-UHFFFAOYSA-N 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
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- C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
- C03C10/0036—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing SiO2, Al2O3 and a divalent metal oxide as main constituents
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- C03C10/0036—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing SiO2, Al2O3 and a divalent metal oxide as main constituents
- C03C10/0045—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing SiO2, Al2O3 and a divalent metal oxide as main constituents containing SiO2, Al2O3 and MgO as main constituents
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- C03C3/087—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal containing calcium oxide, e.g. common sheet or container glass
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Abstract
實施例是關於具有III-V族半導體層的玻璃-陶瓷基板，III-V族半導體層例如是可用於LED照明裝置的GaN層。該玻璃-陶瓷材料是在鈣長石(anorthite)-金紅石(rutile)(CaAl2Si2O8+TiO2)族中或在菫青石(cordierite)-頑火石(enstatite)(SiO2-Al2O3-MgO-TiO2)族中。
Description
本申請案在專利法之下主張美國臨時申請案第61/666,385號的優先權利益，該臨時申請案申請於2012年6月29日。
實施例是關於玻璃-陶瓷基板，且更具體地，是關於用於氮化鎵(GaN,Gallium Nitride)薄膜生長的玻璃-陶瓷基板。
發光二極體(LED)已經商品化超過二十年了，並且具有所欲的特性是包括了能量效率、安全性、小尺寸與長的使用壽命。氮化鎵是用於LED製造的主要材料。
目前，藍寶石(Al2O3,sapphire)與矽是用於LED基板的典型材料。這兩種材料都具有良好的化學與熱耐久性。但是，藍寶石的數量受到限制並且尺寸小於直徑100毫米(mm)才可用，而矽則在尺寸高達直徑300mm為可用。另外，兩種材料在該等材料的熱膨脹係數(CTE,coefficient of thermal expansion)則與GaN有顯著的不同。此種失配會導致基板在生
長期間的彎曲及/或導致GaN結晶品質的高度缺陷。
對於GaN具有優良的CTE匹配，同時也具有優良的熱穩定性(至1100℃)、化學耐久性以及表面拋光特性的替代基板會是有益的。
實施例敘述了一種玻璃-陶瓷基板，該基板適於層轉移與磊晶。該基板在玻璃狀態中製備，形成至所欲的形狀，且之後陶瓷化而結晶。在結晶之後，將該基板拋光至所欲的表面粗糙度，及/或施加平坦層。該基板之後可使用作為接受器，用於轉移例如結晶GaN晶種層。該晶種層在提高的溫度時提供樣板，來用於較厚層的磊晶生長，例如是藉由化學氣相沉積。在進一步處理成元件之後，該基板可選擇性地藉由研磨與拋光而移除，以釋放該等元件。
Corning公司最近已經研發出玻璃-陶瓷的兩種成份族，這兩種成份族對於GaN展現出相當接近的CTE匹配。另外，這些材料具有的所欲特性是：熱穩定至1100℃以及拋光之後的低表面粗糙度。在LED製造處理之後，藉由研磨與拋光可以移除這些材料。這些材料因此可以代表GaN製造性能的階段性改變。
實施例可具有下面的一或多個優點：目前，藍寶石(Al2O3,sapphire)與矽是用於LED基板的主要材料。這兩種材料都具有優良的化學與熱耐久性。但是，藍寶石的數量受到限制並且尺寸小於直徑100mm才可用，而矽則在尺寸高達直徑300mm為可用。另外，兩種材料在該等材料的熱膨脹係數
(CTE)則與GaN有顯著的不同。此種失配會導致基板在生長期間的彎曲及/或導致GaN結晶品質的高度缺陷。
本發明所述的玻璃-陶瓷成份已經修改來匹配GaN的CTE。該等玻璃-陶瓷成份因此在膜缺陷與彎曲方面是優於矽與藍寶石的。因為該等玻璃-陶瓷成份是在高溫時陶瓷化，該等玻璃-陶瓷成份比例如玻璃的其他材料更有熱穩定性，玻璃就無法承受1100℃的使用溫度。該等玻璃-陶瓷成份的小顆粒尺寸允許材料表面可拋光至層轉移與磊晶所需的程度。因為該材料是在玻璃狀態中製備，該技術可縮放至較大的晶圓尺寸與體積。
額外的特徵與優點將提出於下面的詳細說明中，且從該說明，部分內容對於本領域中熟習技藝者來說是相當明顯的，或者藉由實作本文所述的實施例(包括下面的詳細說明、申請專利範圍以及所附圖式)而認出部分內容。
應瞭解到，前面的一般說明與下面的詳細說明都只是範例性的，且是打算來提供用以理解申請專利範圍之特徵與性質的概觀或構架。所附圖式是包括來提供進一步的理解，且所附圖式是併入在本說明書中且構成本說明書的一部分。圖式例示了一或多個實施例，且連同該說明一起用來解釋各種實施例的操作與原理。
第1圖為圖表，針對GaN生長而顯示了目前技術狀態之基板的平均熱膨脹。
第2圖為圖表，顯示了來自鈣長石-金紅石族的範例玻璃-陶瓷
的平均熱膨脹，相較於GaN。
第3圖為圖表，顯示了來自鈣長石-金紅石族的第二範例玻璃-陶瓷的平均熱膨脹，相較於GaN。
第4圖為圖表，顯示了來自菫青石-頑火石族的玻璃-陶瓷的平均熱膨脹，相較於GaN。
第5圖為圖表，顯示了範例2在範例2最終結晶狀態時的X射線繞射(XRD,X-Ray Diffraction)資料。
第6A與6B圖分別為俯視的二次電子顯微鏡(SEM,Secondary Electron Microscopy)與原子力電子顯微鏡(AFM,Atomic Force Microscopy)影像，顯示了大約1微米或更少的結晶顆粒尺寸。
現在將詳細參照玻璃-陶瓷與其在LED物品中之用途的各種實施例，其範例則例示在所附圖式中。盡可能的，相同參考號碼在整個圖式中將是指相同或相似的部件。
一個實施例為一種物品，該物品包括玻璃-陶瓷基板；以及層，該層包括III-V族半導體並且設置於該基板的表面上，其中該基板包括鈣長石-金紅石(CaAl2Si2O8+TiO2)或菫青石-頑火石(SiO2-Al2O3-MgO-TiO2)材料。該III-V族半導體可包括Al、Ga、In或所述者的組合，以及N、P、As或所述者的組合。該III-V族半導體可為GaN、GaP、AlGaAs、InGaAs、InGaN、AlGaP或所述者的組合。該III-V族半導體在一個實施例中為GaN。
另一個實施例為一種物品，該物品包括玻璃-陶瓷基
板；以及層，該層包括GaN並且設置於該基板的表面上，其中該基板包括鈣長石-金紅石(CaAl2Si2O8+TiO2)或菫青石-頑火石(SiO2-Al2O3-MgO-TiO2)材料。
該基板的體積的百分之80或更多可為結晶相，例如，百分之90或更多。該結晶相可分散在該整個體積。該基板的體積的百分之20或更少可為玻璃相，例如，百分之10或更少。該玻璃相可分散在該整個體積。該基板可為例如百分之80或更多的結晶相以及百分之20或更少的玻璃相。
在一個實施例中，GaN層與該基板的CTE是彼此在±5×10-7/℃以內。該基板與該層的CTE，例如在500至1000℃的範圍(例如在選自500、600、700、800、900與1000℃之任兩溫度的範圍)，可各自在55-65×10-7/℃的範圍中，例如，該基板與該層可各自具有大約60×10-7/℃的CTE。
該表面可具有100nm或更少的平均粗糙度，例如，50nm或更少。該基板可具有5微米或更少的平均顆粒尺寸，例如，4微米或更少、3微米或更少、2微米或更少、1微米或更少、0.5微米或更少。
在一個實施例中，該基板無鹼。該基板可無Au、Pd、Ag或Pt，例如，無Au、Pd、Ag與Pt。該基板可無As。在一個實施例中，例如，在升高溫度的後續裝置處理期間或浸在濕化學溶液中，該基板所擴散出的Ni、Na、Cu、Fe、Cr、Ca、Ti、K、Mg或Zn的每一者是少於500ppm。
在一個實施例中，該基板所包括的重量百分比為：a. 15-20 CaO；
b. 30-35 Al2O3；c. 35-40 SiO2；及d. 12-16 TiO2。
如請求項1所述之物品，其中該基板所包括的重量百分比為：e. 40-55 SiO2；f. 10-15 Al2O3；g. 20-30 MgO；h. 1-5 CaO；及i. 5-15 TiO2。
在一個實施例中，該基板所包括的重量百分比為：j. 45-50 SiO2；k. 10-15 Al2O3；l. 20-30 MgO；m. 1-5 CaO；及n. 5-15 TiO2。
在一個實施例中，該基板可具有5mm或更少的厚度，例如4mm或更少、例如3mm或更少、例如2mm或更少、例如1mm或更少、例如0.5mm或更少。該基板可具有0.5mm至4mm的厚度範圍。
玻璃-陶瓷基板可來自鈣長石-金紅石(CaAl2Si2O8+TiO2)族。該成份針對兩範例以氧化物重量百分比給定在表1中。其中，範例2中的該成份是化學計量的。氧化物混合物在1650℃熔化達16小時，之後大量生產成形成物，且在
750℃退火。該等形成物在900℃退火達八小時，以形成晶核，且之後在1250℃結晶達四小時。
在另一實施例中，玻璃-陶瓷是來自菫青石-頑火石(SiO2-Al2O3-MgO-TiO2)族。範例3中的成份以氧化物重量百分比給定在表2中。氧化物混合物在1650℃熔化達16小時，之後大量生產成形成物，且在750℃退火。該等形成物在850℃退火達兩小時，以形成晶核，且之後在1350~1425℃結晶。
在結晶之後，所有三種成份的該等形成物則製作成晶圓並且拋光。
第5圖為圖表，顯示了範例2在範例2最終結晶狀態時的X射線繞射(XRD,X-Ray Diffraction)資料。該資料顯示了兩種結晶相(鈣長石與金紅石)，以及某些殘餘的玻璃物(對於抵消CTE失配所引致的應力是有利的)。
第6A與6B圖分別為俯視的二次電子顯微鏡(SEM,
Secondary Electron Microscopy)與原子力電子顯微鏡(AFM,Atomic Force Microscopy)影像，顯示了大約1微米或更少的結晶顆粒尺寸。這對於表面最後的修整是有利的，因為GaN沉積處理要求-表面必須要完全平滑。
基板上的GaN或GaN自身可用於在例如製造處理中製造LED燈，像是在晶圓尺寸化製作處理中，例如6吋乘6吋或者甚至更大。多個LED可製作在GaN上，且在製作之後分割成單一LED。
對於本領域中熟習技藝者將是明顯的：可對本文所述的實施例作出各種修改與變化，而未偏離所主張之技術特徵的範圍與精神。因此，打算的是，如果此種修改與變化是落在所附申請專利範圍與其均等物的範圍內，則本說明書涵蓋了本文所述的各種實施例的修改與變化。
Claims (19)
- 一種物品，該物品包括一玻璃-陶瓷基板；以及一層，該層包括一III-V族半導體並且設置於該基板的一表面上，其中該基板包括一鈣長石-金紅石(CaAl2Si2O8+TiO2)或一菫青石-頑火石(SiO2-Al2O3-MgO-TiO2)材料。
- 如請求項1所述之物品，其中該III-V族半導體包括Al、Ga、In或所述者的組合，以及N、P、As或所述者的組合。
- 如請求項2所述之物品，其中該III-V族半導體為GaN、GaP、AlGaAs、InGaAs、InGaN、AlGaP或所述者的一組合。
- 如請求項1所述之物品，其中該基板的體積的百分之80或更多是結晶相。
- 如請求項4所述之物品，其中該結晶相是分散在該整個體積。
- 如請求項1所述之物品，其中該基板的體積的百分之20或更少是玻璃相。
- 如請求項6所述之物品，其中該玻璃相是分散在該整個體積。
- 如請求項1所述之物品，其中該層與該基板的該CTE是彼此在±5×10-7/℃以內。
- 如請求項1所述之物品，其中該基板與該層的該CTE是各自在55×10-7/℃與65×10-7/℃之間。
- 如請求項1所述之物品，其中該表面具有100nm或更少的一平均粗糙度。
- 如請求項1所述之物品，其中該基板具有5微米或更少的一平均顆粒尺寸。
- 如請求項1所述之物品，其中該基板無鹼。
- 如請求項1所述之物品，其中該基板無Au、Pd、Ag或Pt。
- 如請求項1所述之物品，其中該基板無Au、Pd、Ag與Pt。
- 如請求項1所述之物品，其中該基板無As。
- 如請求項1所述之物品，其中該基板所擴散出的Ni、 Na、Cu、Fe、Cr、Ca、Ti、K、Mg或Zn的每一者是少於500ppm。
- 如請求項1所述之物品，其中該基板所包括的重量百分比為：15-20 CaO；30-35 Al2O3；35-40 SiO2；及12-16 TiO2。
- 如請求項1所述之物品，其中該基板所包括的重量百分比為：40-55 SiO2；10-15 Al2O3；20-30 MgO；1-5 CaO；及5-15 TiO2。
- 如請求項18所述之物品，其中該基板所包括的重量百分比為：45-50 SiO2；10-15 Al2O3；20-30 MgO；1-5 CaO；及 5-15 TiO2。
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| TWI553919B (zh) * | 2014-04-17 | 2016-10-11 | 康寧精密素材股份有限公司 | 發光二極體之色變換基板及其製造方法 |
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| JP6571389B2 (ja) * | 2015-05-20 | 2019-09-04 | シャープ株式会社 | 窒化物半導体発光素子およびその製造方法 |
| JP6728859B2 (ja) * | 2016-03-25 | 2020-07-22 | 日立金属株式会社 | セラミック基板およびその製造方法 |
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| SG97155A1 (en) * | 1999-07-07 | 2003-07-18 | Hoya Corp | Substrate for information recording medium and magnetic recording medium composed of crystallized glass |
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| TWI553919B (zh) * | 2014-04-17 | 2016-10-11 | 康寧精密素材股份有限公司 | 發光二極體之色變換基板及其製造方法 |
| US9893248B2 (en) | 2014-04-17 | 2018-02-13 | Corning Precision Materials Co., Ltd. | Substrate for changing color of light emitting diode and method for producing same |
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| KR20150036268A (ko) | 2015-04-07 |
| US20140001485A1 (en) | 2014-01-02 |
| EP2867177A1 (en) | 2015-05-06 |
| JP2015528783A (ja) | 2015-10-01 |
| CN104703939A (zh) | 2015-06-10 |
| WO2014004079A1 (en) | 2014-01-03 |
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