CN107002283A - 13族元素氮化物结晶基板及功能元件 - Google Patents
13族元素氮化物结晶基板及功能元件 Download PDFInfo
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- CN107002283A CN107002283A CN201580063728.1A CN201580063728A CN107002283A CN 107002283 A CN107002283 A CN 107002283A CN 201580063728 A CN201580063728 A CN 201580063728A CN 107002283 A CN107002283 A CN 107002283A
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- 239000000758 substrate Substances 0.000 title claims abstract description 121
- 239000013078 crystal Substances 0.000 title claims abstract description 61
- 150000004767 nitrides Chemical class 0.000 title claims abstract description 39
- 230000007547 defect Effects 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims description 43
- 230000012010 growth Effects 0.000 claims description 23
- 229910002601 GaN Inorganic materials 0.000 claims description 21
- 239000002346 layers by function Substances 0.000 claims description 13
- JMASRVWKEDWRBT-UHFFFAOYSA-N Gallium nitride Chemical compound [Ga]#N JMASRVWKEDWRBT-UHFFFAOYSA-N 0.000 claims description 12
- 239000012808 vapor phase Substances 0.000 claims description 11
- 230000004907 flux Effects 0.000 claims description 8
- 239000010410 layer Substances 0.000 description 32
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
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- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 4
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
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- 238000001931 thermography Methods 0.000 description 2
- RGGPNXQUMRMPRA-UHFFFAOYSA-N triethylgallium Chemical compound CC[Ga](CC)CC RGGPNXQUMRMPRA-UHFFFAOYSA-N 0.000 description 2
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910002244 LaAlO3 Inorganic materials 0.000 description 1
- 229910002331 LaGaO3 Inorganic materials 0.000 description 1
- 229910010092 LiAlO2 Inorganic materials 0.000 description 1
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- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910026161 MgAl2O4 Inorganic materials 0.000 description 1
- 229910003200 NdGaO3 Inorganic materials 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 235000005811 Viola adunca Nutrition 0.000 description 1
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- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
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- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
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- 241000894007 species Species 0.000 description 1
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- 229910052725 zinc Inorganic materials 0.000 description 1
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- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
Classifications
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- H—ELECTRICITY
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- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—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
- 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
- H01L33/14—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 with a carrier transport control structure, e.g. highly-doped semiconductor layer or current-blocking structure
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B19/00—Liquid-phase epitaxial-layer growth
- C30B19/02—Liquid-phase epitaxial-layer growth using molten solvents, e.g. flux
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B25/00—Single-crystal growth by chemical reaction of reactive gases, e.g. chemical vapour-deposition growth
- C30B25/02—Epitaxial-layer growth
- C30B25/18—Epitaxial-layer growth characterised by the substrate
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B25/00—Single-crystal growth by chemical reaction of reactive gases, e.g. chemical vapour-deposition growth
- C30B25/02—Epitaxial-layer growth
- C30B25/18—Epitaxial-layer growth characterised by the substrate
- C30B25/20—Epitaxial-layer growth characterised by the substrate the substrate being of the same materials as the epitaxial layer
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
- C30B29/38—Nitrides
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
- C30B29/40—AIIIBV compounds wherein A is B, Al, Ga, In or Tl and B is N, P, As, Sb or Bi
- C30B29/403—AIII-nitrides
- C30B29/406—Gallium nitride
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—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
- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—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
- 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
- H01L33/025—Physical imperfections, e.g. particular concentration or distribution of impurities
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—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
- 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
- H01L33/26—Materials of the light emitting region
- H01L33/30—Materials of the light emitting region containing only elements of Group III and Group V of the Periodic Table
- H01L33/32—Materials of the light emitting region containing only elements of Group III and Group V of the Periodic Table containing nitrogen
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—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
- H01L33/36—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 electrodes
- H01L33/40—Materials therefor
- H01L33/42—Transparent materials
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- 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
- H01S5/02—Structural details or components not essential to laser action
- H01S5/0206—Substrates, e.g. growth, shape, material, removal or bonding
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
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- H01L33/005—Processes
- H01L33/0062—Processes for devices with an active region comprising only III-V compounds
- H01L33/0066—Processes for devices with an active region comprising only III-V compounds with a substrate not being a III-V compound
- H01L33/007—Processes for devices with an active region comprising only III-V compounds with a substrate not being a III-V compound comprising nitride compounds
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- H—ELECTRICITY
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Abstract
结晶基板2由13族元素氮化物结晶构成,且具有第一主面2a及第二主面2b。低载流子浓度区域4和高载流子浓度区域5在第一主面2a与第二主面2b之间延伸。低载流子浓度区域4的载流子浓度为1018/cm3以下,低载流子浓度区域4的缺陷密度为107/cm2以下。高载流子浓度区域5的载流子浓度为1019/cm3以上,高载流子浓度区域6的缺陷密度为108/cm2以上。
Description
技术领域
本发明涉及13族元素氮化物结晶基板及使用了该13族元素氮化物结晶基板的功能元件。本发明能够用在例如要求高品质的技术领域、例如代替荧光灯的被称之为新一代光源的高彩色再现性的白色LED、高速高密度光存储器用蓝紫色激光器、LED前灯、混合动力车用逆变器中使用的大功率器件等之中。
背景技术
随着白色LED的用途扩大,要求LED芯片进一步高性能化。所谓高性能化,是指高效率化、高亮度化。作为氮化镓自立基板的制法,熟知HVPE法。其中,作为得到高品质结晶的方法,公开了DEEP法(专利文献1、非专利文献1)、VAS法(专利文献2、3)。
助熔剂法是液相法中的一种,在氮化镓的情况下,通过使用金属钠作为助熔剂,能够将氮化镓的结晶生长所需的温度缓和到800℃左右,将压力缓和到几MPa。具体而言,氮气溶解到金属钠和金属镓的混合熔液中,氮化镓达到过饱和状态而作为结晶进行生长。这样的液相法因为与气相法相比不容易发生位错,所以能够获得位错密度低的高品质氮化镓。(专利文献4)。
现有技术文献
非专利文献
非专利文献1:SEI Technical Review 2009年7月第175号P.10~18“窒化ガリウム基板の開発(氮化镓基板的开发)”
专利文献
专利文献1:日本特许-3801125
专利文献2:日本特许-3631724
专利文献3:日本特许-4396816
专利文献4:日本特开2009-012986
发明内容
为了制作LED、激光二极管,13族元素氮化物结晶层必须具有高导电性。因此,本发明的发明人尝试在该结晶层中掺杂(dope)Si、氧等掺杂物,由此,使结晶层的导电性得到提高,使得输出增大。
但是,实际上即使增加掺杂物(dopant)量,根据情况,有时也无法得到所希望的发光输出。特别是所谓的纵型发光元件的情况下,有时即使将电压增大某种程度以上、发光强度也不会提高。
本发明的课题是:在13族元素氮化物结晶基板中获得所希望的导电性,并且,有效利用13族元素氮化物结晶的导电性而使功能得到提高。
本发明所涉及的结晶基板是由13族元素氮化物结晶构成且具有第一主面及第二主面的结晶基板,其特征在于,
结晶基板包含:在第一主面与第二主面之间延伸的、低载流子(carrier)浓度区域和高载流子浓度区域,低载流子浓度区域的载流子浓度为1018/cm3以下,低载流子浓度区域的缺陷密度为107/cm2以下,高载流子浓度区域的载流子浓度为1019/cm3以上,高载流子浓度区域的缺陷密度为108/cm2以上。
另外,本发明包括:所述结晶基板、及形成在结晶基板上的功能层,所述功能层由13族元素氮化物形成。
例如,为了制作LED、激光二极管,必须具有高导电性。但是,判明为了赋予导电性而将Si、氧等掺杂物掺杂到13族元素氮化物结晶中时、很难均匀地掺杂到晶片的整面。认为这样的掺杂不均匀性会导致电流泄漏(leakage)。
本发明的发明人为了解决掺杂不均匀性的问题进行了各种研究,但实际上很难解决。不过,在其研究的过程中,发现:对于某种结晶基板,在观察结晶基板的截面时,低载流子浓度区域和高载流子浓度区域分别呈条纹(stripe)状从一方主面朝向另一方主面延伸,并贯穿结晶基板。
即,当在该截面结构的结晶基板上形成纵型LED时,如果将电压提高某种程度以上,则产生因电流泄漏而使得发光强度不会提高的现象。并且,详细地考察了电流泄漏的机制,结果彻底查明了:13族元素氮化物结晶基板的截面结构中,导电性高的区域的结晶性劣化,并且,电流容易流动,因此,局部地发生电流集中,结果导致电流泄漏的发生。即,以显微镜热成像仪(thermography)成功观察到发生电流集中的位置的温度升高。
进而,确认了:在结晶基板的截面结构中,高载流子浓度区域的缺陷也相对较多,容易发生电流泄漏,并且,该高载流子浓度区域以贯穿基板的方式呈条纹状在结晶基板的表面与背面之间进行延伸。同时,确认了:低载流子浓度区域也以贯穿基板的方式呈条纹状在结晶基板的表面与背面之间进行延伸。
应予说明,迄今,施加到LED芯片上的电流密度增加时的发光效率的降低减少被称之为效率下降(droop)现象,有报道称其原因在于载流子溢出(carrier over flow)、非辐射复合、俄歇复合(Auger recombination)等。但是,这些都主要是横型LED结构中的现象。
本发明的发明人发现的上述现象是与效率下降现象不同的现象,迄今完全没有被报道过,是新发现的见解。基于上述观察,首次发现局部发生电流集中。
基于该发现,本发明的发明人尝试:在如上所述的结晶基板的第一主面上形成发光元件结构,此时,将至少一对电极设置在结晶基板的第一主面侧,制作所谓的横型发光元件。发现:这样一来,如上所述的电流泄漏得到抑制、并且获得比较高的发光强度,从而实现本发明。
由此,即使增加施加到结晶基板上的电压也会抑制电流泄漏,因此,能够有效利用结晶基板的导电性而使功能得到提高。
附图说明
图1中,(a)是表示本发明的实施方式所涉及的结晶基板1的剖视简图,(b)是表示另一个实施方式所涉及的结晶基板2的剖视简图。
图2中,(a)表示在支撑基板7上设置有晶种膜8的状态,(b)表示在晶种膜8上设置有由13族元素氮化物结晶构成的结晶基板1的状态。
具体实施方式
以下,适当参照附图,对本发明进一步进行说明。
(结晶基板)
优选的实施方式中,如图1(a)、(b)所示,提供由13族元素氮化物构成的结晶基板1、2。结晶基板1、2分别包含:在第一主面1a、2a与第二主面1b、2b之间贯穿的低载流子浓度区域4和高载流子浓度区域5。确认了各区域4、5分别是在第一主面与第二主面之间贯穿结晶基板1、2而生成的。
此处,低载流子浓度区域4的载流子浓度为1018/cm3以下,低载流子浓度区域4的缺陷密度为107/cm2以下。另外,高载流子浓度区域5的载流子浓度为1019/cm3以上,高载流子浓度区域5的缺陷密度为108/cm2以上。由前述的机制发现:掺杂物集中在高载流子浓度区域从而使得载流子浓度升高,并且,缺陷也集中在相同区域,且在结晶基板的主面之间以贯穿结晶基板的方式进行延伸。
此处,低载流子浓度区域的载流子浓度优选为5×1017/cm3以下。另外,存在如上所述的高载流子浓度区域的结晶基板中,低载流子浓度区域的载流子浓度多数为1×1016/cm3以上。另外,低载流子浓度区域的缺陷密度优选为5×106/cm2以下。另外,低载流子浓度区域的缺陷密度多数为1×106/cm2以上。
另外,高载流子浓度区域的载流子浓度为1019/cm3以上,优选为2×1019/cm3以上。另外,存在如上所述的低载流子浓度区域的结晶基板中,高载流子浓度区域的载流子浓度多数为1×1020/cm3以下。另外,高载流子浓度区域的缺陷密度优选为1×109/cm2以下。
此处,掺杂物为n型掺杂物(Si、Ge、氧等)的情况下,由于活化率高达98%以上,所以可以将掺杂物浓度看作载流子浓度。以下,从防止由电流集中导致的泄漏的本发明的观点考虑,记载为“载流子浓度”,但是,还可以将活化率视为100%,将其称为“掺杂物浓度”。
本发明中,如下测定并识别高载流子浓度区域及低载流子浓度区域。
使用阴极发光测定器(例如、(株)堀场制作所制MP系列),倍率为50~500倍,使图像拍摄区域为0.1~1mm见方。
按照实施例中记载的方法及条件来测定载流子浓度及缺陷密度。
构成结晶基板的13族元素是指IUPAC制定的元素周期表中的第13族元素。13族元素具体为镓、铝、铟、铊等。该13族元素氮化物特别优选为氮化镓、氮化铝、氮化镓铝。另外,作为添加剂,可以举出:碳、低熔点金属(锡、铋、银、金)、高熔点金属(铁、锰、钛、铬等过渡金属)。
从操作(把持)的观点考虑,结晶基板的厚度优选为250μm以上,更优选为300μm以上。另外,从经济性及导电性的观点考虑,结晶基板的厚度优选为450μm以下。
(功能层及功能元件)
通过在结晶基板上形成规定的功能层,能够得到功能元件。
该功能层可以为单层,也可以为多层。另外,作为功能,可用于高亮度·高彩色再现性的白色LED、高速高密度光存储器用蓝紫色激光光盘、混合动力汽车用逆变器中使用的大功率器件等。
在结晶基板上,通过气相法、优选有机金属气相生长(MOCVD)法制作半导体发光二极管(LED)时,LED内部的位错密度与结晶基板的位错密度是等同的。
例如,从抑制引入碳等不需要的杂质的观点考虑,功能层的成膜温度优选为950℃以上,更优选为1000℃以上。另外,从抑制缺陷的观点考虑,功能层的成膜温度优选为1200℃以下,更优选为1150℃以下。
功能层的材质优选13族元素氮化物。13族元素是指IUPAC制定的元素周期表中的第13族元素。13族元素具体为镓、铝、铟、铊等。
发光元件结构例如具备n型半导体层、设置在该n型半导体层上的发光区域以及设置在该发光区域上的p型半导体层。另外,上述发光元件结构中可以进一步设置没有图示的n型半导体层用的电极、p型半导体层用的电极、导电性接合层、缓冲层、导电性支撑体等。
本发光元件结构中,如果通过从半导体层注入的空穴和电子的复合而在发光区域发光,则从p型半导体层上的透光性电极或13族元素氮化物单晶膜侧引出光。应予说明,透光性电极是指形成在p型半导体层的几乎整面的由金属薄膜或透明导电膜形成的光透过性的电极。
构成n型半导体层、p型半导体层的半导体的材质包括III-V族系化合物半导体,可以列举如下材料。
AlyInxGa1-x-yN(0≤x≤1、0≤y≤1)
作为用于赋予n型导电性的掺杂材料,可以举出硅、锗、氧。另外,作为用于赋予p型导电性的掺杂材料,可以举出镁、锌。
构成发光结构的各半导体层的生长方法可以举出各种气相生长方法。例如可以采用有机金属化合物气相生长法(MOCVD(MOVPE)法)、分子束外延法(MBE法)、氢化物气相生长法(HVPE法)等。其中,利用MOCVD法时,能够得到各半导体层的结晶性、平坦度良好的产品。MOCVD法中,作为Ga源,多使用TMG(三甲基镓)、TEG(三乙基镓)等烷基金属化合物,作为氮源,使用氨、肼等气体。
发光区域包含量子阱活性层。量子阱活性层的材料设计成带隙比n型半导体层以及p型半导体层的材料小。量子阱活性层可以为单一量子阱(SQW)结构,也可以为多量子阱(MQW)结构。量子阱活性层的材质可以列举如下。
作为量子阱活性层的优选例,可以举出将作为AlxGa1-xN/AlyGa1-yN系量子阱活性层(x=0.15、y=0.20)的、膜厚分别为3nm/8nm的量子阱活性层以3~10个周期形成而得到的MQW结构。
本发明对于所谓的横型功能元件、特别是发光元件而言是优选的。
此处,关于横型功能元件,在本发明的结晶基板的第一主面上形成功能元件结构时,将至少一对驱动电极设置在结晶基板的第一主面侧。因此,向电极之间施加电压时,朝向与结晶基板的第一主面大致平行的方向施加电场。
本发明的结晶基板中,在三维观察时为柱状的高载流子浓度区域和低载流子浓度区域朝向第一主面与第二主面之间进行延伸,因此,如果与主面大致平行地施加电压,则电场交替通过多个高载流子浓度区域和低载流子浓度区域。结果,抑制了电极之间的漏电流,能够发挥与电压相对应的功能。
(结晶基板的制造)
优选的实施方式中,在晶种上形成结晶基板。晶种可以由其自身形成自立基板(支撑基板)或者也可以为形成在另一支撑基板上的晶种膜。该晶种膜可以为一层或者也可以在支撑基板侧包含缓冲层。
例如图2(a)所示,在支撑基板7的表面7a形成晶种膜8。晶种膜8包含13族元素氮化物。
在支撑基板上形成晶种膜的情况下,对构成支撑基板的单晶的材质没有限定,可以举出:蓝宝石、AlN模板、GaN模板、GaN自立基板、硅单晶、SiC单晶、MgO单晶、尖晶石(MgAl2O4)、LiAlO2、LiGaO2、LaAlO3,LaGaO3,NdGaO3等钙钛矿型复合氧化物、SCAM(ScAlMgO4)。另外,也可以使用组成式〔A1-y(Sr1-xBax)y〕〔(Al1-zGaz)1-u·Du〕O3(A为稀土元素;D为从由铌及钽构成的组中选择的一种以上元素;y=0.3~0.98;x=0~1;z=0~1;u=0.15~0.49;x+z=0.1~2)的立方晶系的钙钛矿结构复合氧化物。
13族元素氮化物结晶层的培养方向可以是纤锌矿结构的c面的法线方向,另外也可以是a面、m面各自的法线方向。
从降低设置在晶种上的结晶基板的位错密度的观点考虑,希望在晶种表面8a的位错密度低。从该观点考虑,晶种的位错密度优选为7×108cm-2以下,更优选为5×108cm-2以下。另外,从品质方面考虑,晶种的位错密度越低越良好,所以,对下限没有特别限定,一般多为5×107cm-2以上。
晶种的制法没有特别限定,可以举出:有机金属化学气相生长(MOCVD:MetalOrganic Chemical Vapor Deposition)法、氢化物气相生长(HVPE)法、脉冲激发堆积(PXD)法、MBE法、升华法等气相法、助熔剂法等液相法。
接下来,如图2(b)所示,在晶种8上形成结晶基板1。
优选的实施方式中,通过助熔剂法培养结晶基板1。此时,助熔剂的种类只要能够生成13族元素氮化物即可,没有特别限定。优选的实施方式中,使用包含碱金属和碱土金属中的至少一方的助熔剂,特别优选包含金属钠的助熔剂。
在助熔剂中混合13族元素的原料物质,进行使用。作为该原料物质,可使用金属单质、合金、化合物,从操作方面考虑,优选13族元素的金属单质。
以助熔剂法形成结晶基板的情况下,为了促进纵向的生长,使过饱和度尽可能地低,并且抑制熔液的对流,由此,使其尽量仅以浓度梯度为驱动力进行结晶生长。从而,抑制核的形成,自核朝向上方进行结晶生长。
具体而言,优选通过以下方法培养结晶基板。
(1A)通过提高坩埚内的熔液的平均培养温度来减小过饱和度,从而抑制核的形成。
(2A)通过将坩埚的上部保持在比坩埚的底部高的温度来抑制熔液在坩埚内的对流。
(3A)不对熔液进行搅拌,或者减小搅拌速度。
(4A)降低含氮气体的分压。
例如,可适用如下条件。
(1A)使坩埚内的熔液的平均培养温度为870~885℃。
(2A)保持坩埚的上部的温度比坩埚的底部的温度高0.5~1℃。
(3A)不对熔液进行搅拌,或者使搅拌速度为30rpm以下。另外,使搅拌方向为单向。
(4A)使含氮气体的分压为3.5~3.8MPa。
该条件下,在高载流子浓度区域内存在更多的结晶缺陷。这是因为:以柱状自下而上结晶生长的结构中,掺杂物较多的部位存在载流子、结晶缺陷均增加的倾向。
此处所称的结晶缺陷是指穿透位错(Threading Dislocation),其包括螺旋位错(screw dislocation)、刃型位错(edge dislocation)、及它们的混合位错(mixeddislocation)这3种。可以通过透射电子显微镜(TEM)或者阴极发光(CL)来确认这些位错。
助熔剂法中,在包含含有氮原子的气体的气氛下对单晶进行培养。该气体优选为氮气,也可以为氨气。气氛中的含有氮原子的气体以外的气体没有限定,优选为惰性气体,特别优选为氩气、氦气、氖气。
在上述的(1A)~(4A)的条件下,优选保持1小时以上,更优选保持2小时以上。
另外,还可以在(1A)~(4A)的条件下培养后设置像下面的(1B)~(4B)这样的培养阶段。
(1B)使坩埚内的熔液的平均培养温度比(1A)阶段低。例如可以使坩埚内的熔液的平均培养温度为850~865℃。
(2B)通过将坩埚的上部的温度保持在坩埚的底部的温度以下,促进熔液在坩埚内的对流。例如保持坩埚的上部的温度比坩埚的底部的温度低0.5~1℃。
(3B)使熔液的搅拌速度为30rpm以上,并使搅拌方向定期反转。
(4B)使含氮气体的分压比(4A)阶段中的分压高。例如使含氮气体的分压为3.9~4.2MPa。
从本发明的观点考虑,优选熔液中的13族元素氮化物/助熔剂(例如钠)的比率(mol比率)高,优选为18mol%以上,更优选为25mol%以上。但是,如果该比例变得过大,则结晶品质有下降的倾向,所以,优选为40mol%以下。
(气相法)
例如HVPE法的情况下,在生长初期阶段,使氢混合比高(例如50%以上),使生长速度慢(例如10~20微米/hr),成为自核朝向上方优先生长的状态。
以助熔剂法生长的13族元素氮化物,在照射波长330~385nm的光(例如汞灯的光)时,发出在波长440~470nm处具有峰的较宽的荧光(蓝色的荧光)。与此相对,通过气相法制作的13族元素氮化物,在照射波长330~385nm的光时,发出在波长540~580nm处具有峰的较宽的荧光(黄色的荧光)。因此,能够通过照射波长330~385nm的光时发出的荧光的颜色来区分由助熔剂法得到的13族元素氮化物和由气相法得到的13族元素氮化物。
(结晶层的加工及形态)
如图2(b)所示,在晶种8上形成结晶基板1后,可以在结晶基板的第一主面1a上形成规定的功能层。或者,通过磨削加工、剥离法等从晶种8上除去结晶基板1,由此,如图1(a)所示,能够分离出结晶基板1。这种情况下,在分离得到的结晶基板1的第一主面1a上设置规定的功能层。此时,通过对结晶基板的第二主面1b实施研磨加工,能够减少结晶基板的翘曲。
或者,对结晶基板1的表面1a进行研磨,由此,如图1(b)所示,能够使结晶基板2的第一主面2a成为研磨面。另外,此时,通过对结晶基板1的第二主面1b实施研磨加工,能够使结晶基板2的第二主面2b成为研磨面。
优选的实施方式中,13族元素氮化物结晶层为圆形板状,也可以为方板等其它形态。另外,优选的实施方式中,结晶层的尺寸为直径以上。由此,能够提供适合功能元件的量产、操作容易的结晶层。
就对结晶基板的第一主面、第二主面进行磨削、研磨加工的情况进行说明。
磨削(grinding)是指一边使将研磨粒子用粘合剂固定而得到的固定研磨粒子高速旋转,一边使其接触对象物,对对象物的表面进行磨削。通过这样的磨削,形成粗糙面。在对氮化镓基板的底面进行磨削的情况下,优选使用包含由硬度高的SiC、Al2O3、金刚石以及CBN(立方氮化硼、下同)等形成的、粒径为10μm~100μm左右的研磨粒子的固定研磨粒子。
另外,研磨(lapping)是指使平台和对象物间隔着游离研磨粒子(没有被固定的研磨粒子、下同)彼此边旋转边接触,或使固定研磨粒子和对象物彼此边旋转边接触,对对象物的表面进行研磨。通过这样的研磨,能够形成面粗糙度比磨削时小且比微研磨(polishing)时粗糙的面。优选使用由硬度高的SiC、Al2O3、金刚石以及CBN等形成的、粒径为0.5μm~15μm左右的研磨粒子。
微研磨(polishing)是指使研磨垫和对象物间隔着游离研磨粒子彼此边旋转边接触,或使固定研磨粒子和对象物彼此边旋转边接触,对对象物的表面进行微细研磨而平滑化。通过这样的微研磨,能够形成面粗糙度比研磨时小的结晶生长面。
实施例
(实施例1)
按照参照图1~图2说明的顺序,制作结晶基板2及横型发光元件。
(晶种基板的制造)
使用MOCVD法,在直径2英寸、厚度500μm的c面蓝宝石基板7上,于530℃沉积低温GaN缓冲层20nm,然后,于1050℃层叠厚度2μm的由GaN形成的晶种膜8。通过TEM(透射型电子显微镜)进行观察得到的缺陷密度为1×109/cm2。用有机溶剂、超纯水分别超声波清洗10分钟后,进行干燥,将其作为晶种基板。
(结晶基板的生长)
在填充有惰性气体的手套箱中,按摩尔比20:80称量金属Ga和金属Na,与晶种基板一同配置在氧化铝制坩埚的底部。进而,作为掺杂物,添加相对于Ga而言为1mol/cm3的量的液体锗原料。将3个该坩埚堆起来,在最上面的坩埚上盖上氧化铝制盖子。将这些坩埚收纳在不锈钢制保持容器(内部容器)中,再将4个收纳有多个坩埚的该内部容器堆起来,收纳在不锈钢制保持容器(内容器)中。
接下来,通过使设置在耐压容器内部的加热器发热,使坩埚内的原料熔解,产生Ga-Na混合熔液。一边加热使坩埚温度为880℃,一边从氮气瓶中导入氮气直至3.8MPa,开始结晶生长。5小时后,将坩埚温度经20小时降温至850℃,使压力变为4.0MPa,同时开始通过旋转台的连续反转进行搅拌,使其进行结晶生长。旋转条件如下:使其以30rpm的速度绕着中心轴以一定周期的顺时针和逆时针进行旋转。加速时间=6秒、保持时间=200秒、减速时间=6秒、停止时间=1秒。在该状态下保持24小时。GaN结晶的厚度增加了约300微米。
通过对得到的结晶基板1的表面1a进行研磨加工,使厚度为150微米。通过阴极发光(以下简称为CL)法测定表面的100微米见方区域中的黑点密度,结果为2×105/cm2。将该黑点密度作为缺陷密度。通过霍尔测定来测定从该结晶板上切出为6mm见方的样品的载流子浓度,结果为5×1018/cm3。
另外,由汞灯对得到的氮化镓结晶基板照射波长330~385nm的光时,发出在440~470nm处具有峰的较宽的荧光(蓝色的荧光)。
(晶片的制作)
然后,对基板进行激光剥离加工,将支撑基板7及晶种膜8从结晶基板1上分离出来。通过机械加工及干法刻蚀对结晶基板1的两面1a、1b实施平坦加工,制作厚度250μm的2英寸晶片(结晶基板)2。
利用CL观察该结晶基板2的截面结构。结果,分为明亮发光的区域5和较暗区域4,在截面处进行观察时可知均以条纹状生长。另外,在明亮发光的区域5的中心部确认到起因于位错集中部的暗线。明亮发光的区域5的缺陷密度为2~5×108/cm2,载流子浓度为1×1019/cm3。发光强度较弱的区域4的缺陷密度大体均匀,为2×106/cm2,载流子浓度为5×1017/cm3。
应予说明,关于载流子浓度,使用预先通过涡流方式测定判明的5个样品(1×1017/cm3、5×1017/cm3、1×1018/cm3、5×1018/cm3、1×1019/cm3)进行CL测定,将其图像的亮度以8位色(255个色阶)进行图像处理,对于载流子浓度与CL图像的亮度的关系,制作校正曲线。使用校正曲线,计算出载流子浓度。
(发光元件的制作)
使用得到的结晶基板,利用MOCVD法制作LED结构,然后,形成电极图案,对背面进行背面抛光(back polishing)。背面抛光后的结晶基板的厚度为70微米。然后,通过切割(dicing)制作1mm见方的横型结构的蓝色LED。测定350mA驱动时的内部量子效率,结果得到约80%的高值。发光强度在面内是均匀的。进而,使驱动电流增加至1000mA,测定其内部量子效率,结果维持65%的高值。另外,施加2V时的漏电流低至5nA。
另外,使用得到的结晶基板,利用MOCVD法制作LED结构,然后,形成电极图案,对背面进行背面抛光。背面抛光后的结晶基板的厚度为70微米。然后,通过切割制作1mm见方的纵型结构的蓝色LED。
关于得到的纵型LED元件,测定350mA驱动时的内部量子效率,结果得到约75%的比较高的值,但发光强度在面内不均匀。进而,使其增加至1000mA测定其内部量子效率,结果降低至55%,发光强度不均更加明显。另外,施加2V时的漏电流为0.1μA,较大。
由以上的实验结果可知:基底层的明亮发光区域5中的缺陷集中部构成漏电流的原因。
(实施例2)
与实施例1同样地得到晶种基板。通过气相法在该晶种基板上制作结晶基板。
(气相法GaN结晶生长)
III族原料使用镓(Ga)和氯化氢(HCl)的反应生成物、即氯化镓(GaCl),V族原料使用氨气(NH3),通过氢化物VPE法培养氮化镓结晶。将晶种基板放置在氢化物VPE的生长装置中,在氨气氛下升温到生长温度1000℃。生长温度稳定后,以40cc/分钟的流量供给HCl,以1000cc/分钟的流量供给NH3、并且以0.01cc/分钟的流量供给硅烷(SiH4),使n型的GaN结晶进行生长。
在该状态下保持4小时,在氨气氛下冷却至常温,从生长装置中取出,结果GaN结晶生长了约300微米。
通过对得到的结晶基板1的表面1a进行研磨加工,使厚度为250微米。利用CL法测定表面的黑点密度,结果为8×106/cm2。将该黑点密度作为缺陷密度。通过霍尔测定来测定从该结晶基板上切出为6mm见方的样品的载流子浓度,结果为5×1018/cm3。
(晶片的制作)
然后,对基板进行激光剥离加工,将支撑基板7及晶种膜8从结晶基板1上分离出来。通过机械加工及干法刻蚀对结晶基板1的两面1a、1b实施平坦加工,制作厚度250μm的2英寸晶片(结晶基板)2。
利用CL观察该结晶基板2的截面结构。结果,分为明亮发光的区域5和较暗区域4,在截面处进行观察可知均以条纹状进行生长。另外,在明亮发光的区域5的中心部确认到起因于位错集中部的暗线。明亮发光的区域5的缺陷密度为2×108/cm2,载流子浓度为2×1019/cm3。发光强度较弱的区域5的缺陷密度大体均匀,为5×105/cm2,载流子浓度为8×1017/cm3。
另外,由汞灯对得到的氮化镓结晶板照射波长330~385nm的光时,发出在540~580nm处具有峰的较宽的荧光(黄色的荧光)。
(发光元件的制作)
使用得到的结晶基板,利用MOCVD法制作LED结构,然后,形成电极图案,对背面进行背面抛光。背面抛光后的结晶基板的厚度为70微米。然后,通过切割制作1mm见方的横型结构的蓝色LED。测定350mA驱动时的内部量子效率,结果得到约80%的高值。发光强度在面内是均匀的。进而,使驱动电流增加至1000mA测定其内部量子效率,结果维持65%的高值。另外,施加2V时的漏电流低至5nA。
另外,使用得到的结晶基板,利用MOCVD法制作LED结构,然后,形成电极图案,对背面进行背面抛光。背面抛光后的结晶基板的厚度为70微米。然后,通过切割制作1mm见方的纵型结构的蓝色LED。
关于得到的纵型LED元件,测定350mA驱动时的内部量子效率,结果得到75%的比较高的值,但发光强度在面内不均匀。进而,使其增加至1000mA测定其内部量子效率,结果降低至55%,发光强度不均更加明显。另外,施加2V时的漏电流为1μA,较大。
Claims (8)
1.一种13族元素氮化物结晶基板,其是由13族元素氮化物结晶构成且具有第一主面及第二主面的结晶基板,其特征在于,
所述结晶基板包含:在所述第一主面与所述第二主面之间延伸的、低载流子浓度区域和高载流子浓度区域,所述低载流子浓度区域的载流子浓度为1018/cm3以下,所述低载流子浓度区域的缺陷密度为107/cm2以下,所述高载流子浓度区域的载流子浓度为1019/cm3以上,所述高载流子浓度区域的缺陷密度为108/cm2以上。
2.根据权利要求1所述的13族元素氮化物结晶基板,其特征在于,
所述13族元素氮化物结晶基板的厚度为250μm~450μm。
3.根据权利要求1或2所述的13族元素氮化物结晶基板,其特征在于,
所述13族元素氮化物结晶基板通过助熔剂法或气相法形成。
4.根据权利要求1~3中的任意一项所述的13族元素氮化物结晶基板,其特征在于,
所述13族元素氮化物结晶基板的所述第一主面为研磨面。
5.根据权利要求1~4中的任意一项所述的13族元素氮化物结晶基板,其特征在于,
构成所述13族元素氮化物结晶基板的所述13族元素氮化物结晶由氮化镓形成。
6.一种功能元件,其特征在于,
所述功能元件包括:权利要求1~5中的任意一项所述的13族元素氮化物结晶基板、及形成在所述13族元素氮化物结晶基板上的功能层,所述功能层由13族元素氮化物形成。
7.根据权利要求6所述的功能元件,其特征在于,
所述功能层具有发光功能。
8.根据权利要求7所述的功能元件,其特征在于,
所述功能元件为横型发光元件。
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