JP2008108759A - Nitride material manufacturing method - Google Patents
Nitride material manufacturing method Download PDFInfo
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- JP2008108759A JP2008108759A JP2006287160A JP2006287160A JP2008108759A JP 2008108759 A JP2008108759 A JP 2008108759A JP 2006287160 A JP2006287160 A JP 2006287160A JP 2006287160 A JP2006287160 A JP 2006287160A JP 2008108759 A JP2008108759 A JP 2008108759A
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- gadolinium
- aluminum nitride
- aluminum
- metal plate
- thin film
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- 239000000463 material Substances 0.000 title claims abstract description 16
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 15
- 150000004767 nitrides Chemical class 0.000 title claims abstract description 15
- 229910052688 Gadolinium Inorganic materials 0.000 claims abstract description 82
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 claims abstract description 81
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 53
- 239000000758 substrate Substances 0.000 claims abstract description 48
- 238000004544 sputter deposition Methods 0.000 claims abstract description 43
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 claims abstract description 40
- 239000013077 target material Substances 0.000 claims abstract description 33
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 31
- 239000010703 silicon Substances 0.000 claims abstract description 31
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 29
- 239000011261 inert gas Substances 0.000 claims description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 abstract description 62
- 229910052786 argon Inorganic materials 0.000 abstract description 39
- 239000007789 gas Substances 0.000 abstract description 38
- 239000010409 thin film Substances 0.000 abstract description 36
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 35
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 30
- 229910052751 metal Inorganic materials 0.000 abstract description 30
- 239000002184 metal Substances 0.000 abstract description 30
- 238000001228 spectrum Methods 0.000 abstract description 6
- 229910052782 aluminium Inorganic materials 0.000 description 24
- PIGFYZPCRLYGLF-UHFFFAOYSA-N Aluminum nitride Chemical compound [Al]#N PIGFYZPCRLYGLF-UHFFFAOYSA-N 0.000 description 22
- 239000013078 crystal Substances 0.000 description 18
- -1 argon ions Chemical class 0.000 description 17
- 239000010408 film Substances 0.000 description 10
- 238000001755 magnetron sputter deposition Methods 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- UVYDYKVLJBNFFS-UHFFFAOYSA-N aluminum gadolinium Chemical compound [Al].[Gd] UVYDYKVLJBNFFS-UHFFFAOYSA-N 0.000 description 5
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 5
- 230000001133 acceleration Effects 0.000 description 4
- 230000005684 electric field Effects 0.000 description 4
- 238000010894 electron beam technology Methods 0.000 description 4
- 229910002601 GaN Inorganic materials 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 230000003595 spectral effect Effects 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- JMASRVWKEDWRBT-UHFFFAOYSA-N Gallium nitride Chemical compound [Ga]#N JMASRVWKEDWRBT-UHFFFAOYSA-N 0.000 description 2
- RNQKDQAVIXDKAG-UHFFFAOYSA-N aluminum gallium Chemical compound [Al].[Ga] RNQKDQAVIXDKAG-UHFFFAOYSA-N 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
- 239000010980 sapphire Substances 0.000 description 2
- 229910052594 sapphire Inorganic materials 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000001659 ion-beam spectroscopy Methods 0.000 description 1
- 229910052743 krypton Inorganic materials 0.000 description 1
- DNNSSWSSYDEUBZ-UHFFFAOYSA-N krypton atom Chemical compound [Kr] DNNSSWSSYDEUBZ-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 229910052704 radon Inorganic materials 0.000 description 1
- SYUHGPGVQRZVTB-UHFFFAOYSA-N radon atom Chemical compound [Rn] SYUHGPGVQRZVTB-UHFFFAOYSA-N 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
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- Physical Deposition Of Substances That Are Components Of Semiconductor Devices (AREA)
Abstract
ã課é¡ã 宀枩ã§ã¹ãã¯ãã«å¹
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ãã§ããçªåç©ææããäœã³ã¹ãã§è£œé ã§ããè£œé æ¹æ³ãæäŸããã
ãè§£æ±ºææ®µã ã¢ã«ãããŠã é屿¿ïŒïŒïŒãšã¬ããªããŠã é屿¿ïŒïŒïŒãšãã¿ãŒã²ããææãšããã¢ã«ãŽã³ãçªçŽ æ··åã¬ã¹ïŒïŒã®é°å²æ°äžã§ã¹ããã¿ãªã³ã°ãè¡ãããšã§ã¬ããªããŠã æ·»å ã®çªåã¢ã«ãããŠã èèã補é ããããŸããçªåã¢ã«ãããŠã é屿¿ïŒïŒïŒåã³ã¬ããªããŠã é屿¿ïŒïŒïŒãã¿ãŒã²ããææãšããã¢ã«ãŽã³ã¬ã¹ïŒïŒã®é°å²æ°äžã§ã¹ããã¿ãªã³ã°ãè¡ãããšã§ã¬ããªããŠã æ·»å ã®çªåã¢ã«ãããŠã èèã補é ããã奜ãŸããã¯ãã·ãªã³ã³åºæ¿ïŒïŒäžã«èèã圢æããã
ãéžæå³ãå³ïŒPROBLEM TO BE SOLVED: To provide a manufacturing method capable of manufacturing a nitride material capable of high-efficiency ultraviolet light emission having a narrow spectrum width at room temperature at low cost.
A gadolinium-added aluminum nitride thin film is produced by performing sputtering in an atmosphere of a mixed gas of argon and nitrogen using an aluminum metal plate 641 and a gadolinium metal plate 642 as target materials. Further, a gadolinium-added aluminum nitride thin film is manufactured by performing sputtering in an atmosphere of argon gas 68 using the aluminum nitride metal plate 643 and the gadolinium metal plate 642 as target materials. Preferably, a thin film is formed on the silicon substrate 66.
[Selection] Figure 1
Description
æ¬çºæã¯ãçªåç©ææã®è£œé æ¹æ³ã«é¢ããç¹ã«çŽ«å€é åã§çºå ããããšã®ã§ããçªåç©ææã®è£œé æ¹æ³ã«é¢ããã   The present invention relates to a method for manufacturing a nitride material, and more particularly to a method for manufacturing a nitride material capable of emitting light in the ultraviolet region.
çŸåšã玫å€çºå ãã€ãªãŒããªã©ã®åºäœçŽ åã®çŽ«å€çºå ããã€ã¹ã¯ãåºäœç §æçšå±èµ·å æºãè¶ é«éç©å èšé²ããã€ã¹çšå æºãèšæž¬çšæ°äœã¬ãŒã¶ãŒçœ®ãæããç°å¢æ±æç©è³ªã«å¯Ÿããå è§Šåªåè§£åŠçå æºã殺èçšå æºããã€ãªãå»åŠå¿çšãªã©ãæ§ã ãªå¿çšåéãæåŸ ãããŠãããããã§ãåŸæ¥ãããçªåã¬ãªãŠã ïŒïŒ§ïœïŒ®ïŒãšçªåã¢ã«ãããŠã ïŒïŒ¡ïœïŒ®ïŒã®æ··æ¶åå°äœã§ããçªåã¢ã«ãããŠã ã»ã¬ãªãŠã ïŒïŒ¡ïœïŒ§ïœïŒ®ïŒãçšãã玫å€çºå ããã€ã¹ã掻çºã«ææ¡ãããŠããïŒäŸãã°ãéç¹èš±æç®ïŒïŒããã®ãããªçªåã¢ã«ãããŠã ã»ã¬ãªãŠã ïŒïŒ¡ïœïŒ§ïœïŒ®ïŒã¯ãäŒå°åž¯ãã䟡é»å垯ãžã®é»åã®é·ç§»ã«ããçŠå¶åž¯å¹ ã«çžåœãããšãã«ã®ãŒã玫å€çºå ããã   Currently, solid-state ultraviolet light-emitting devices such as ultraviolet light-emitting diodes are used as solid-state excitation light sources, ultra-high integrated optical recording device light sources, gas lasers for measurement, photocatalytic decomposition treatment light sources for environmental pollutants, sterilization light sources, bio Various application fields such as medical applications are expected. Therefore, an ultraviolet light emitting device using aluminum nitride gallium (AlGaN) which is a mixed crystal semiconductor of gallium nitride (GaN) and aluminum nitride (AlN) has been actively proposed (for example, Non-Patent Document 1). . Such aluminum gallium nitride (AlGaN) emits ultraviolet light with energy corresponding to the forbidden band width due to the transition of electrons from the conduction band to the valence band.
ããããçªåã¢ã«ãããŠã ã»ã¬ãªãŠã ïŒïŒ¡ïœïŒ§ïœïŒ®ïŒãçšãã玫å€çºå ããã€ã¹ã¯ãé»åã®å ãããšãã«ã®ãŒäœçœ®ãç±çã«åºãã£ãŠããããŸããçŠå¶åž¯äžã®äžçŽç©ãšãã«ã®ãŒäœçœ®ã«é»åãèœã¡èŸŒãããšãããã宀枩ã§ãã¹ãã¯ãã«å¹ ãçãé«å¹çãªçŽ«å€çºå ãåŸãããšã¯å°é£ã§ãã£ãã   However, in the ultraviolet light emitting device using aluminum gallium nitride (AlGaN), the energy position occupied by the electrons is thermally spread, and the electrons may fall into the impurity energy position in the forbidden band. It has been difficult to obtain highly efficient ultraviolet light emission with a narrow spectrum width.
ããã§ãæ°ãã«ãçªåã¢ã«ãããŠã ïŒïŒ¡ïœïŒ®ïŒã«ã¬ããªããŠã ïŒïŒ§ïœïŒãæ·»å ãã玫å€çºå
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ããã€ã¹ã®è£œé æ¹æ³ãšããŠã¯ãçŸåšãååç·ãšãã¿ãã·ã£ã«æé·æ³ïŒïŒïŒ¢ïŒ¥æ³ïŒãçšããŠçåçªçŽ ïŒïŒ³ïœïŒ£ïŒåºæ¿äžã«åçµæ¶èãäœæãããã®ã®ã¿ãç¥ãããŠããã
ããããªãããäžè¿°ã®ååç·ãšãã¿ãã·ã£ã«æé·æ³ïŒïŒïŒ¢ïŒ¥æ³ïŒã¯ãæ¶²äœçªçŽ çã®å·åŽè£ 眮ãè¶ é«ç空ãå®çŸã§ããææ°ç³»ãã³ããå«ãè€éãªè£ 眮ãå¿ èŠãšãããã®ã§ãããè£ çœ®ã®è£œé ã³ã¹ãåã³æ¶²äœçªçŽ çãå©çšããããšã«ããã©ã³ãã³ã°ã³ã¹ãçã®å€ãã®è²»çšãå¿ èŠãšããããŸããåºæ¿ãšããŠçšããçåçªçŽ ïŒïŒ³ïœïŒ£ïŒã¯ãäžè¬ã«è¯ãçšããããã·ãªã³ã³ïŒïŒ³ïœïŒçã«æ¯ã¹ãŠé«äŸ¡ã§ãããã®ç¹ã§ãè²»çšã倧ãããªãã   However, the molecular beam epitaxial growth method (MBE method) described above requires a complicated device including a cooling device such as liquid nitrogen and an exhaust system pump capable of realizing an ultra-high vacuum. A lot of expenses such as running cost by using etc. are required. Further, silicon carbide (SiC) used as a substrate is more expensive than silicon (Si) or the like that is generally used, and this also increases the cost.
ããã§æ¬çºæã¯ã宀枩ã§ã¹ãã¯ãã«å¹ ã®çãé«å¹çã®çŽ«å€çºå ãã§ããçªåç©ææããäœãè²»çšã§è£œé ã§ããè£œé æ¹æ³ãæäŸããããšãç®çãšããã   Accordingly, an object of the present invention is to provide a manufacturing method capable of manufacturing a nitride material capable of high-efficiency ultraviolet light emission having a narrow spectrum width at room temperature at a low cost.
äžèšç®çãéæããããã«ãè«æ±é ïŒã«èšèŒã®çºæã«ãããçªåç©ææè£œé æ¹æ³ã¯ãã¢ã«ãããŠã ãšã¬ããªããŠã ãšãã¿ãŒã²ããææãšããäžæŽ»æ§ã¬ã¹ã«çªçŽ ãæ··å ¥ããé°å²æ°äžã§ã¹ããã¿ãªã³ã°ãè¡ãå·¥çšãæããããšãç¹åŸŽãšããŠããã   In order to achieve the above object, a method for producing a nitride material according to the first aspect of the invention includes a step of performing sputtering in an atmosphere in which aluminum and gadolinium are used as target materials and nitrogen is mixed in an inert gas. It is characterized by that.
è«æ±é ïŒã«èšèŒã®çºæã«ä¿ãçªåç©ææè£œé æ¹æ³ã¯ãçªåã¢ã«ãããŠã åã³ã¬ããªããŠã ãã¿ãŒã²ããææãšããã¹ããã¿ãªã³ã°ãè¡ãå·¥çšãæããããšãç¹åŸŽãšããŠããã   A method for producing a nitride material according to a second aspect of the invention includes a step of performing sputtering using aluminum nitride and gadolinium as target materials.
è«æ±é ïŒã«èšèŒã®çºæã«ä¿ãçªåç©ææè£œé æ¹æ³ã¯ãã·ãªã³ã³ãåºæ¿ã«çšããŠã¹ããã¿ãªã³ã°ãè¡ãããšç¹åŸŽãšããŠããã   The nitride material manufacturing method according to claim 3 is characterized in that sputtering is performed using silicon as a substrate.
è«æ±é ïŒã®çºæã«ä¿ãæ¹æ³ã«ãããšãã¢ã«ãããŠã ãšã¬ããªããŠã ãšãã¿ãŒã²ããææãšããäžæŽ»æ§ã¬ã¹ã«çªçŽ ãæ··å ¥ããé°å²æ°äžã§ã¹ããã¿ãªã³ã°ãè¡ãããšã§ãã¬ããªããŠã ïŒïŒ§ïœïŒãæ·»å ããçªåã¢ã«ãããŠã ïŒïŒ¡ïœïŒ®ïŒèèãçæã§ãããã¹ããã¿ãªã³ã°ã¯ãæ¯èŒçç°¡åãªèšåã§è¡ãããšãã§ããã®ã§ã宀枩ã§ã¹ãã¯ãã«å¹ ã®çãé«å¹çã®çŽ«å€çºå ãã§ããçªåç©ææã§ããã¬ããªããŠã ïŒïŒ§ïœïŒãæ·»å ãããçªåã¢ã«ãããŠã ïŒïŒ¡ïœïŒ®ïŒããäœãè²»çšã§è£œé ã§ããã   According to the method of the first aspect of the present invention, an aluminum nitride (AlN) thin film to which gadolinium (Gd) is added by sputtering in an atmosphere in which aluminum and gadolinium are used as target materials and nitrogen is mixed in an inert gas. Can be generated. Since sputtering can be performed with relatively simple equipment, aluminum nitride (AlN) to which gadolinium (Gd), which is a nitride material capable of high-efficiency ultraviolet light emission with a narrow spectral width at room temperature, is added, has a low cost. Can be manufactured.
è«æ±é ïŒã®çºæã«ä¿ãæ¹æ³ã«ãããšãçªåã¢ã«ãããŠã ãšã¬ããªããŠã ãšãã¿ãŒã²ããææãšããäžæŽ»æ§ã¬ã¹ã®ã¿ã«é°å²æ°äžã§ã¹ããã¿ãªã³ã°ãè¡ãããšã§ãã¬ããªããŠã ãæ·»å ããçªåã¢ã«ãããŠã èèãçæã§ãããã¹ããã¿ãªã³ã°ã¯ãæ¯èŒçç°¡åãªèšåã§è¡ãããšãã§ããã®ã§ãé°å²æ°ã«çªçŽ ãæ··å ¥ããªããšãã宀枩ã§ã¹ãã¯ãã«å¹ ã®çãé«å¹çã®çŽ«å€çºå ãã§ããçªåç©ææã§ããã¬ããªããŠã ïŒïŒ§ïœïŒãæ·»å ãããçªåã¢ã«ãããŠã ïŒïŒ¡ïœïŒ®ïŒããäœãè²»çšã§è£œé ã§ããã   According to the method of the second aspect of the present invention, an aluminum nitride thin film to which gadolinium is added can be generated by performing sputtering in an atmosphere only with an inert gas using aluminum nitride and gadolinium as target materials. Sputtering can be performed with relatively simple equipment, so gadolinium (Gd), which is a nitride material capable of high-efficiency ultraviolet light emission with a narrow spectrum width at room temperature, without adding nitrogen to the atmosphere was added. Aluminum nitride (AlN) can be produced at low cost.
è«æ±é ïŒã®çºæã«ãããšãã·ãªã³ã³ãåºæ¿ã«çšããã®ã§ãçåçªçŽ çãåºæ¿ã«çšããå Žåã«æ¯ã¹ãŠãå®äŸ¡ãªçªåç©ææãæäŸããããšãã§ããã   According to the invention of claim 3, since silicon is used for the substrate, an inexpensive nitride material can be provided as compared with the case where silicon carbide or the like is used for the substrate.
以äžãæ¬çºæã®å®æœåœ¢æ ã«ã€ããŠå³é¢ãåç §ãã€ã€èª¬æããããŸããæ¬çºæã®ç¬¬ïŒã®å®æœåœ¢æ ãšããŠãã¢ã«ãããŠã (ïœïŒãšã¬ããªããŠã ïŒïŒ§ïœïŒãšãã¿ãŒã²ããææãšããçªçŽ ïŒïŒ®ïŒãšã¢ã«ãŽã³ïŒïŒ¡ïœïŒãå«ãé°å²æ°äžã§é«åšæ³¢ãã°ãããã³ã¹ããã¿ãè¡ãããšã«ãããã·ãªã³ã³ïŒïŒ³ïœïŒåºæ¿äžã«ã¬ããªããŠã ïŒïŒ§ïœïŒãæ·»å ãããçªåã¢ã«ãããŠã ïŒïŒ¡ïœïŒ®ïŒèèã圢æããå Žåã«ã€ããŠèª¬æããã   Embodiments of the present invention will be described below with reference to the drawings. First, as a first embodiment of the present invention, silicon (Si) is obtained by performing high-frequency magnetron sputtering in an atmosphere containing nitrogen (N) and argon (Ar) using aluminum (Al) and gadolinium (Gd) as target materials. A case where an aluminum nitride (AlN) thin film to which gadolinium (Gd) is added is formed on a (Si) substrate will be described.
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  As shown in FIG. 1, the high-frequency
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  In the first embodiment, a
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  When the gadolinium (Gd) -added aluminum nitride (AlN) thin film is formed by using the high-frequency
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  In this way, when high frequency power is applied, plasma containing argon ions is generated. The argon ions are accelerated by an electric field generated by applying high-frequency power and collide with the
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  In the second embodiment, as the
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  When forming an aluminum nitride (AlN) thin film added with gadolinium (Gd), first, the inside of the
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  In this way, when high frequency power is applied, plasma containing argon ions is generated. The argon ions are accelerated by an electric field generated by applying high-frequency power and collide with the aluminum
次ã«ãæ¬çºæã®ç¬¬ïŒã®å®æœåœ¢æ ãšããŠãã¢ã«ãããŠã ïŒïŒ¡ïœïŒãšã¬ããªããŠã ïŒïŒ§ïœïŒãæ··åããŠã¿ãŒã²ããææãšããçªçŽ ïŒïŒ®ïŒãšã¢ã«ãŽã³ïŒïŒ¡ïœïŒãå«ãé°å²æ°äžã§çŽæµé»æºãçšããïŒæ¥µã¹ããã¿ãè¡ãããšã«ãããã·ãªã³ã³ïŒïŒ³ïœïŒåºæ¿äžã«ã¬ããªããŠã ïŒïŒ§ïœïŒãæ·»å ããçªåã¢ã«ãããŠã ïŒïŒ¡ïœïŒ®ïŒèèã圢æããå Žåã«ã€ããŠèª¬æããã   Next, as a third embodiment of the present invention, a target material is prepared by mixing aluminum (Al) and gadolinium (Gd), and a DC power source is used in an atmosphere containing nitrogen (N) and argon (Ar) 2. A case where an aluminum nitride (AlN) thin film to which gadolinium (Gd) is added is formed on a silicon (Si) substrate by pole sputtering will be described.
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  In the third embodiment, an aluminum and gadolinium
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  When a gadolinium-added (Gd) aluminum nitride (AlN) thin film is formed using the
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  In this way, when DC power is applied, plasma containing argon ions is generated. The argon ions are accelerated by an electric field generated by applying DC power and collide with the
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  In the fourth embodiment, an aluminum nitride and gadolinium
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  When a gadolinium-added (Gd) aluminum nitride (AlN) thin film is formed, first, the pressure in the
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  In this way, when DC power is applied, plasma containing argon ions is generated. The argon ions are accelerated by an electric field generated by applying DC power and collide with the aluminum
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  The sputtering apparatus used for sputtering according to the present invention is not limited to the high-frequency
ãŸããæ¬çºæã«ä¿ãã¹ããã¿ãªã³ã°ã«çšããåºæ¿ã¯ãäžè¿°ã®ã·ãªã³ã³ïŒïŒ³ïœïŒåºæ¿ã奜é©ã«çšãããããããã«éããããã®ã§ã¯ãªããäŸãã°ããµãã¡ã€ã¢åºæ¿ãçåçªçŽ ïŒïŒ³ïœïŒ£ïŒåºæ¿ãªã©ãçšããããšãã§ããããªããã·ãªã³ã³ïŒïŒ³ïœïŒã¯ä»ã®åºæ¿ææã«æ¯ã¹ãŠå®äŸ¡ã§ããããŸããåºç¯ã«æ®åããŠãããæè¡ã®å¿çšã«ãããä¿¡é Œæ§ãé«ãã®ã§æ¬çºæã®åºæ¿ãšããŠå¥œé©ã«çšããããšãã§ããããŸãããµãã¡ã€ã¢ã¯ãä»ã®åºæ¿ææãšç°ãªãæ³¢é·ïŒïŒïŒããã¡ãŒãã«ã®çŽ«å€å ãééããããšãã§ããã®ã§ãããé«å¹çã®çŽ«å€å çºå ãå®çŸããããšãã§ããããŸããçåçªçŽ ïŒïŒ³ïœïŒ£ïŒã¯ç±çãååŠçãæ©æ¢°çå®å®æ§ã«åªããŠããã®ã§ã髿ž©ç°å¢ã«ããããå Žåãè¬åèæ§ãæ±ããããå Žåãªã©ã«ã¯ã奜é©ã«çšããããã   The substrate used for sputtering according to the present invention is preferably the above-mentioned silicon (Si) substrate, but is not limited thereto. For example, a sapphire substrate or a silicon carbide (SiC) substrate can be used. Note that silicon (Si) is less expensive than other substrate materials, is widely spread, and has high reliability in application of technology, so that it can be suitably used as the substrate of the present invention. In addition, unlike other substrate materials, sapphire can transmit ultraviolet light having a wavelength of 350 nanometers, so that more efficient ultraviolet light emission can be realized. Silicon carbide (SiC) is excellent in thermal, chemical, and mechanical stability, and is therefore preferably used when placed in a high temperature environment or when chemical resistance is required.
ãŸããæ¬çºæã«ä¿ãã¹ããã¿ãªã³ã°ã«çšããé°å²æ°ã¬ã¹ã¯ãäžè¿°ã®çªçŽ ãšã¢ã«ãŽã³ãšã®æ··åã¬ã¹ã«éããããã®ã§ã¯ãªããäŸãã°ãã¢ã«ãŽã³ïŒïŒ¡ïœïŒã«å€ããŠãããªãŠã ïŒïŒšïœ ïŒãããªã³ïŒïŒ®ïœ ïŒãã¯ãªããã³ïŒïŒ«ïœïŒããã»ãã³ïŒïŒžïœ ïŒãã©ãã³ïŒïŒ²ïœïŒãªã©ã®åžã¬ã¹ãçšããŠããããããªãã¡ãã¢ã«ãããŠã ïŒïŒ¡ïœïŒåã³ã¬ããªããŠã ïŒïŒ§ïœïŒãšæ®ã©åå¿ããªãæ°äœã§ãã£ãŠããã©ãºããçºçãæãæ°äœã§ããã°ããã   Moreover, the atmospheric gas used for sputtering according to the present invention is not limited to the above-mentioned mixed gas of nitrogen and argon. For example, a rare gas such as helium (He), neon (Ne), krypton (Kr), xenon (Xe), or radon (Rn) may be used instead of argon (Ar). That is, any gas that hardly reacts with aluminum (Al) and gadolinium (Gd) and that easily generates plasma may be used.
ãŸãã第ïŒã®å®æœåœ¢æ åã³ç¬¬ïŒã®å®æœåœ¢æ ã§ãè¿°ã¹ãããã«ãé°å²æ°ã¬ã¹ãšããŠåžã¬ã¹ã®ã¿ãçšããçªçŽ ãæ³šå ¥ããªããã®ã§ãã£ãŠãããããã®å Žåãã¿ãŒã²ãããšããŠãçªåã¢ã«ãããŠã åã³ã¬ããªããŠã ãçšããããšã§çªåã¢ã«ãããŠã ã¬ããªããŠã èèãçæããããšãã§ããã   Further, as described in the second embodiment and the fourth embodiment, only the rare gas may be used as the atmospheric gas and nitrogen may not be injected. In this case, an aluminum gadolinium nitride thin film can be generated by using aluminum nitride and gadolinium as targets.
æ¬çºæã®ã¹ããã¿ãªã³ã°ãè¡ããšãã®åºæ¿ã®æž©åºŠã¯å®€æž©ïŒææ°ïŒïŒåºŠïŒããææ°ïŒïŒïŒåºŠã®éã§ããããšã奜ãŸãããåºæ¿æž©åºŠãå®€æž©ïŒææ°ïŒïŒåºŠïŒæªæºã§ãããšãåºæ¿ã«å ç©ããçªåã¢ã«ãããŠã ã¬ããªããŠã èèã®è³ªãæªããªãããŸããåºæ¿æž©åºŠãææ°ïŒïŒïŒåºŠãè¶ ãããšåºæ¿ã«çªåã¢ã«ãããŠã ã¬ããªããŠã èèã圢æããã«ãããªãããã§ããããŸããæ¬çºæã®ã¹ããã¿ãªã³ã°ãè¡ããšãã®é°å²æ°ã¬ã¹ã®ã¬ã¹å§ã¯ïŒïŒïŒïŒ°ïœä»¥äžïŒïŒ°ïœä»¥äžã®ç¯å²å ã§ããããšã奜ãŸããã   The temperature of the substrate when performing sputtering of the present invention is preferably between room temperature (27 degrees Celsius) and 200 degrees Celsius. When the substrate temperature is lower than room temperature (27 degrees Celsius), the quality of the aluminum gadolinium thin film deposited on the substrate is deteriorated, and when the substrate temperature exceeds 200 degrees Celsius, the aluminum nitride gadolinium thin film is hardly formed on the substrate. Because. Moreover, it is preferable that the gas pressure of atmospheric gas when performing sputtering of this invention exists in the range of 0.1 Pa or more and 1 Pa or less.
ãŸããæ¬çºæã®ã¹ããã¿ãªã³ã°ã«ãããŠãã¿ãŒã²ããææãšããŠã¢ã«ãããŠã ãšã¬ããªããŠã ã䜿çšããå Žåã®é°å²æ°ã¬ã¹äžã«å«ãŸããã¢ã«ãŽã³ãšçªçŽ ãšã®æ¯çã¯ãã¢ã«ãŽã³ãïŒãšãããšãã«çªçŽ ãïŒä»¥äžïŒïŒïŒä»¥äžã®ç¯å²ãšãªãããšã奜ãŸãããã¢ã«ãŽã³ã®å²åãäœããããšãã©ãºããçºçãã«ãããªããå¹ççãªèèçæãã§ããªããªãããŸããçªçŽ ã®å²åãäœããããšã¹ããã¿ãªã³ã°ãããŠé°å²æ°äžã«é£ã³åºããã¢ã«ãããŠã åã³ã¬ããªããŠã ãçªçŽ ã€ãªã³ãšåå¿ãã«ãããªããããçªåã¢ã«ãããŠã ã¬ããªããŠã èèã圢æããã«ãããªãã   In the sputtering of the present invention, the ratio of argon and nitrogen contained in the atmospheric gas when aluminum and gadolinium are used as the target material is such that nitrogen is 1 or more and 1.5 or less when argon is 1. It is preferable that If the proportion of argon is too low, plasma is difficult to generate and efficient thin film generation cannot be achieved. On the other hand, if the proportion of nitrogen is too low, aluminum and gadolinium that are sputtered and jumped out into the atmosphere are difficult to react with nitrogen ions, so that an aluminum nitride gadolinium thin film is hardly formed.
ãŸããã¿ãŒã²ããææå šäœã«å¯Ÿããã¬ããªããŠã ã®é鿝çã¯ïŒããŒã»ã³ã以äžïŒïŒããŒã»ã³ã以äžã奜ãŸãããã¬ããªããŠã ã®é鿝çãïŒããŒã»ã³ãæªæºã§ãããšãçæãããçªåã¢ã«ãããŠã ã¬ããªããŠã èèäžã«å«ãŸããã¬ããªããŠã ã®å«æéãå°ãªããªããããé«å¹çã®çŽ«å€çºå ãã§ããªããªãããŸããã¬ããªããŠã ã®é鿝çã倧ãããªãããã¢ã«ãããŠã ã®é鿝çãå°ãããªãããããšãçªåã¢ã«ãããŠã ã¬ããªããŠã èèã®è³ªãäœäžããã   Further, the weight ratio of gadolinium to the entire target material is preferably 2% or more and 50% or less. When the weight ratio of gadolinium is less than 2 percent, the content of gadolinium contained in the produced aluminum gadolinium thin film is reduced, so that highly efficient ultraviolet light emission cannot be performed. Further, when the weight ratio of gadolinium is increased and the weight ratio of aluminum is too small, the quality of the aluminum nitride gadolinium thin film is deteriorated.
ãŸããæ¬çºæã®ã¿ãŒã²ããææã«å°å ãããé»åã¯ïŒïŒïŒã¯ãã以äžïŒïŒïŒïŒã¯ãã以äžã奜ãŸãããå°å ãããé»åãäœããããšããã©ãºãã®çºçãã¹ããã¿ãªã³ã°ãããã«ãããªãããŸããé»åãé«ããããšã¿ãŒã²ããåã³åºæ¿ã髿ž©ã«ãªãããããæŽã«ãæ¬çºæã«ãããŠã¯ã補èæéã¯ïŒïŒå以äžïŒïŒïŒå以äžã§ããããšã奜ãŸããã   The power applied to the target material of the present invention is preferably 200 watts or more and 2000 watts or less. If the applied power is too low, it is difficult to generate plasma or perform sputtering. On the other hand, if the power is too high, the target and the substrate become too hot. Furthermore, in the present invention, the film formation time is preferably 15 minutes or longer and 120 minutes or shorter.
以äžã®æ¡ä»¶ã®ããšã¹ããã¿ãªã³ã°ããããªããšèåïŒïŒïŒããã¡ãŒãã«ä»¥äžïŒïŒïŒïŒããã¡ãŒãã«ä»¥äžã®çªåã¢ã«ãããŠã ã¬ããªããŠã èèãçæãããããã®ããã«ããŠçæããçªåã¢ã«ãããŠã ã¬ããªããŠã èèã¯ãå ç©ããŠããã¬ããªããŠã ãå³ïŒã«ç€ºãããã«ãã®ååå ã«æããå æ®»ãšãã«ã®ãŒæºäœã®ïŒïœå±èµ·æºäœããïŒïœåºåºæºäœãžã®é»åã®é·ç§»ã«ãããçŽïŒïŒïŒããã¡ãŒãã«ã®æ³¢é·ã®ã¹ãã¯ãã«å¹ ã®çã玫å€çºå ãå¯èœãšãªãã   When sputtering is performed under the above conditions, an aluminum gadolinium thin film having a film thickness of 200 nanometers or more and 1200 nanometers or less is generated. The aluminum gadolinium nitride thin film thus produced is formed by the transition of electrons from the 6p excited level of the core energy level of the deposited gadolinium in the atom to the 8s ground level as shown in FIG. , It is possible to emit ultraviolet light with a narrow spectral width at a wavelength of about 315 nanometers.
次ã«ãæ¬çºæã®å ·äœç宿œãªå®æœäŸã説æããããªããæ¬çºæã¯ä»¥äžã«ç€ºã宿œäŸã«éå®ããããã®ã§ãªãããšã¯äºããŸã§ããªãã   Next, specific embodiments of the present invention will be described. Needless to say, the present invention is not limited to the following examples.
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[Example 1]
In Example 1, as shown in Table 1, the high-frequency
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[Example 2]
In Example 2, as shown in FIG. 3, a counter type
宿œäŸïŒã®ã¹ããã¿ãªã³ã°ã®çµæãã·ãªã³ã³åçµæ¶ãŠãšãã®ïŒïŒïŒïŒïŒçµæ¶é¢ãïŒã§èгå¯ãããšãããèåçŽïŒïŒïŒïŒããã¡ãŒãã«ã®è¡šé¢å¹³åŠãªãã¬ããªããŠã ãå«ãçªåã¢ã«ãããŠã èèãåºæ¿å šé¢ã«èгå¯ã§ããããã®è©Šæãç·åæïŒX-ray diffractionïŒïŒžïŒ²ïŒ€ïŒã§èª¿ã¹ããšãããå³ïŒã«ç€ºãç·åæåŒ·åºŠã®ã°ã©ããåŸããããå³ïŒã«ãããšãã·ãªã³ã³åºæ¿ä»¥å€ã«çªåã¢ã«ãããŠã ããã®åæããŒã¯ãããäºãåããããŸããåŸãããèã宀枩ã§ïŒïŒãããã«ãã®å éé»å§ãçšããŠé»åç·ç §å°ãããšãããå³ïŒã«ç€ºãããã«æ³¢é·ïŒïŒïŒããã¡ãŒãã«åã³ïŒïŒïŒããã¡ãŒãã«ã«çºå ããŒã¯ãããæçãªçŽ«å€çºå ãèŠãããã   As a result of sputtering in Example 2, when the (111) crystal plane of the silicon single crystal wafer was observed with an SEM, a flat surfaced aluminum nitride thin film containing gadolinium having a thickness of about 1200 nanometers could be observed on the entire surface of the substrate. When this sample was examined by X-ray diffraction (XRD), a graph of X-ray diffraction intensity shown in FIG. 7 was obtained. According to FIG. 7, it can be seen that there is a diffraction peak from aluminum nitride other than the silicon substrate. Further, when the obtained film was irradiated with an electron beam at room temperature using an acceleration voltage of 10 kilovolts, clear ultraviolet emission having emission peaks at wavelengths of 313 nanometers and 318 nanometers was seen as shown in FIG. .
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[Example 3]
In Example 3, the gas pressure of the atmosphere in the
宿œäŸïŒã®ã¹ããã¿ãªã³ã°ã®çµæãã·ãªã³ã³åçµæ¶ãŠãšãã®ïŒïŒïŒïŒïŒçµæ¶é¢ãïŒã§èгå¯ãããšãããèåçŽïŒïŒïŒããã¡ãŒãã«ã®è¡šé¢å¹³åŠãªãã¬ããªããŠã ãå«ãçªåã¢ã«ãããŠã èèãåºæ¿å šé¢ã«èгå¯ã§ãããåŸãããèã宀枩ã§ïŒïŒãããã«ãã®å éé»å§ãçšããŠé»åç·ç §å°ãããšãããå³ïŒã«ç€ºãããã«æ³¢é·ïŒïŒïŒããã¡ãŒãã«ã«çºå ããŒã¯ãããæçãªçŽ«å€çºå ã芳å¯ã§ããã   As a result of sputtering in Example 3, when the (111) crystal plane of the silicon single crystal wafer was observed with an SEM, a flat surfaced aluminum nitride thin film containing gadolinium having a film thickness of about 500 nm could be observed on the entire surface of the substrate. When the obtained film was irradiated with an electron beam at an acceleration voltage of 10 kilovolts at room temperature, clear ultraviolet light emission having a light emission peak at a wavelength of 312 nanometers was observed as shown in FIG.
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[Example 4]
In Example 4, the gas pressure of the atmosphere in the chamber 7 was set to 0.76 Pascal, and the temperature of the silicon single crystal wafer was controlled to 100 degrees Celsius. Also, 1000 watts of DC power was applied for 100 minutes. The other points were performed under the same conditions as in Example 2.
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以äžã®å®æœäŸïŒãã宿œäŸïŒã瀺ãããã«ãã¿ãŒã²ãããšããŠã¢ã«ãããŠã åã³ã¬ããªããŠã ãçšããçªçŽ ãå«ãé°å²æ°ã¬ã¹äžã§ã¹ããã¿ãªã³ã°ããããšã§ãã¬ããªããŠã ãå«ãçªåã¢ã«ãããŠã èèãã·ãªã³ã³åºæ¿å šé¢ã«çæããããšãã§ããããããŠããã®ã¬ããªããŠã ãå«ãçªåã¢ã«ãããŠã èèã¯æ³¢é·ïŒïŒïŒããã¡ãŒãã«ããïŒïŒïŒããã¡ãŒãã«ã®ç¯å²å ã«çºå ããŒã¯ãæããã   As shown in Examples 1 to 4 above, an aluminum nitride thin film containing gadolinium can be formed on the entire surface of the silicon substrate by sputtering in an atmosphere gas containing nitrogen using aluminum and gadolinium as targets. . The aluminum nitride thin film containing gadolinium has a light emission peak within a wavelength range of 310 to 320 nanometers.
ãªãã宿œäŸïŒããïŒã«ã¯ç€ºããŠããªãããã¿ãŒã²ãããšããŠçªåã¢ã«ãããŠã åã³ã¬ããªããŠã ãçšããŠãçªçŽ ãæ®ã©å«ãŸãªãé°å²æ°ã¬ã¹äžã§ã¹ããã¿ãªã³ã°ããããšã§ããã¬ããªããŠã ãå«ãçªåã¢ã«ãããŠã èèãã·ãªã³ã³åºæ¿å šé¢ã«çæããããšãã§ããããã®å Žåã宿œäŸïŒããïŒãšåæ§ã®èèã圢æãããããšãšãªãã®ã§ãåœç¶ã«æ³¢é·ïŒïŒïŒããã¡ãŒãã«ããïŒïŒïŒããã¡ãŒãã«ã®ç¯å²å ã«çºå ããŒã¯ãæããããšãšãªãã   Although not shown in Examples 1 to 4, an aluminum nitride thin film containing gadolinium is formed on the entire surface of the silicon substrate by sputtering in an atmosphere gas containing almost no nitrogen using aluminum nitride and gadolinium as targets. can do. In this case as well, a thin film similar to that in Examples 1 to 4 is formed, and naturally, the emission peak is in the wavelength range of 310 to 320 nanometers.
å ã¯æ³¢é·ãïŒïŒïŒããã¡ãŒãã«ããïŒïŒïŒããã¡ãŒãã«ã®éã§çŽ«å€çºå ããããïŒïŒïŒããã¡ãŒãã«ä»è¿ã®çãæ³¢é·ã®çŽ«å€å ã§ã¯ã¬ã³ãºã«å¯Ÿããééæ§ãäœããªããæ§ã ãªäœ¿çšãå¶éãããåé¡ãããããŸããïŒïŒïŒããã¡ãŒãã«ä»è¿ã®æ³¢é·ã®çŽ«å€å ã§ã¯å¯èŠå ã«è¿ããªããååŠåå¿ãèµ·ããã«ãããªãã®ã§ãåçš®åéã§ã®å¿çšãé£ãããªããæ¬çºæã«ãã補é ãããã¬ããªããŠã ãå«ãçªåã¢ã«ãããŠã èèã¯ãå®€æž©ã§æ³¢é·ïŒïŒïŒããã¡ãŒãã«ããïŒïŒïŒããã¡ãŒãã«ãŸã§ã®ã¹ãã¯ãã«å¹ ã®çãé«å¹çã®çŽ«å€çºå ãã§ããã®ã§ãäžè¿°ã®ãããªåé¡ããªããæ§ã ãªæè¡åéã«å¿çšããããšãã§ããã   Light emits ultraviolet light at a wavelength of 250 to 350 nanometers. However, ultraviolet light having a short wavelength around 250 nanometers has a problem that the transmittance to the lens is low and various uses are restricted. In addition, ultraviolet light having a wavelength of around 350 nanometers is close to visible light, making it difficult for chemical reactions to occur, making application in various fields difficult. The aluminum nitride thin film containing gadolinium produced according to the present invention can emit high-efficiency ultraviolet light having a narrow spectral width from a wavelength of 310 nm to 320 nm at room temperature. Can be applied in the field.
æ¬çºæã¯ãäŸãã°çŽ«å€çºå ãã€ãªãŒãã®è£œé ã«çšããããšãã§ããã   The present invention can be used, for example, in the manufacture of ultraviolet light emitting diodes.
ïŒïŒ ã¿ãŒã²ããææ
ïŒïŒïŒ ã¢ã«ãããŠã é屿¿ïŒïŒ¡ïœïŒ
ïŒïŒïŒ ã¬ããªããŠã é屿¿ïŒïŒ§ïœïŒ
ïŒïŒïŒ çªåã¢ã«ãããŠã é屿¿ïŒïŒ¡ïœïŒ®ïŒ
ïŒïŒ ã·ãªã³ã³åºæ¿ïŒïŒ³ïœïŒ
ïŒïŒ ã¢ã«ãŽã³ãçªçŽ æ··åã¬ã¹ïŒïŒ¡ïœãïŒ
ïŒïŒ ã¢ã«ãŽã³ã¬ã¹ïŒïŒ¡ïœïŒ
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64
642 Gadolinium metal plate (Gd)
643 Aluminum nitride metal plate (AlN)
66 Silicon substrate (Si)
67 Argon and nitrogen mixed gas (Ar, N)
68 Argon gas (Ar)
780 Aluminum and gadolinium mixed metal plate (Al, Gd)
781 Aluminum nitride, gadolinium mixed metal plate (AlN, Gd)
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4555899B2 (en) * | 2007-09-03 | 2010-10-06 | åœç«å€§åŠæ³äººç¥æžå€§åŠ | Deep ultraviolet semiconductor optical device |
| JP2018041967A (en) * | 2010-12-16 | 2018-03-15 | ã¢ãã©ã€ã ãããªã¢ã«ãº ã€ã³ã³ãŒãã¬ã€ãããïœïœïœïœïœ ïœ ïŒïœïœïœ ïœïœïœïœïœïŒïŒ©ïœïœïœïœïœïœïœïœïœïœ ïœ | Gallium nitride-based led fabrication with pvd-formed aluminum nitride buffer layer |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4555899B2 (en) * | 2007-09-03 | 2010-10-06 | åœç«å€§åŠæ³äººç¥æžå€§åŠ | Deep ultraviolet semiconductor optical device |
| JPWO2009031584A1 (en) * | 2007-09-03 | 2010-12-16 | åœç«å€§åŠæ³äººç¥æžå€§åŠ | Deep ultraviolet semiconductor optical device |
| JP2018041967A (en) * | 2010-12-16 | 2018-03-15 | ã¢ãã©ã€ã ãããªã¢ã«ãº ã€ã³ã³ãŒãã¬ã€ãããïœïœïœïœïœ ïœ ïŒïœïœïœ ïœïœïœïœïœïŒïŒ©ïœïœïœïœïœïœïœïœïœïœ ïœ | Gallium nitride-based led fabrication with pvd-formed aluminum nitride buffer layer |
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