578209 五、發明說明（1 ) 【技術領域】 本發明係有關一種利用P型或η型導電性或高電阻的 磷化硼系半導體層、以構成磷化硼系化合物半導體元件之 技術。 【先前技術】 自古以來，一種I I I - V族化合物半導體爲磷化硼（ΒΡ ) 係爲已知（參照寺本嚴著、「半導體裝置槪論」（ 1 995年 3月30日、（股）培風館發行、28頁））。磷化硼係爲菲利 普斯之離子鍵結度（=δ)爲0.006之小値幾乎全爲雙鍵性之 半導體（Phillips著、「半導體鍵結論」（參照1 985年7 月25曰、（股）吉岡書店發行第3刷、51頁））。同時，磷 化硼由於爲立方晶之閃鋅礦（z i n c - b 1 end )型結晶（參照上 述之「半導體裝置槪論」、28頁）、與氮化鎵（GaN)等之六 方纖鐵礦（Wii r t z i t e )型半導體結晶不同價電子帶縮帶（參 照生駒俊明、生駒英明共著、「化合物半導體之基礎物 性入門」）（1 99 1年9月1 0日、（股）培風館發行、出版）、 14〜17頁）。因此，磷化硼例如與離子鍵結度（δ)爲0.50 之高纖鐵礦結晶形GaN相比（參照上述「半導體鍵結 論」、51頁），具有容易製得p型傳導層之基本特徵。 依照該特徵，習知的p型磷化硼半導體層例如雷射二 極管（LD )，利用於爲設有電極之接觸層（參照特開平1 〇 -242 5 67號公報）。而且，揭示由在砷化鎵（GaP)、碳化矽 (S i C )、或GaN單結晶基板上具備p型磷化硼層作爲緩衝 578209 五、發明說明（2) 層的積層構造體構成LD或發光二極管（LED)之技術。另外， 使添加有p型雜質之磷化硼與氮化鋁•鎵（AlxGa]_xN ·· 〇 ‘ X $ 1 )之混晶作爲發光層構成發光元件之習知例（參照特 開平2 - 27 5 682號）。習知技術中p型磷化硼層係使p型雜 質以鎂（Mg)、或鋅（Zn)等之有機金屬熱分解氣相成長法 .(M0CVD)法形成（參照美國專利6,069,021號）。 然而，故意不添加雜質、所謂的未摻雜（undope)之磷 化硼中，被稱爲存在有占有硼之空孔（vacancy)的碟之可 能性（參照庄野克房著、「超LS I時代之半導體技術1 00 集ΠΙΙ ]」（股）歐姆（譯音）公司、昭和57年4月1日發 行、「電子雜誌電子學」、第27卷4頁（昭和57年4月 號）附錄電子學文庫18、86〜87頁）。換言之，揭示存在 占有硼之正規格子位置的磷原子之可能性。另外，揭示存 在占有磷之空孔之的硼之可能性。占有立方晶閃鋅礦之磷 化硼的正規格子位置之磷係具有施體（dono r )作用（參照上 述「超LSI時代之半導體技術[III ]」、86〜87頁）。反之， 占有憐之正規格子的硼係具有受體作用（參照上述「超LS I 時代之半導體技術[III]」、86〜87頁）。 【發明內容】 如上所述，揭示磷化硼層中含有抗區分地段（8111卜 s ! t e )之可能性（參照生駒俊明、生駒英明共著、「化合 物半導體之基礎物性入門」）（股）培風館、（1 99 1年9月 1 0日發行初版）、1 4 1頁）。抗區分地段缺陷由於係有關 578209 五、發明說明（3) 構成元素之硼（B)及憐（P)之缺陷，故多量存在。因此，例 如在存在有多量作爲施體作用之占有硼的空格子點之磷狀 態下，即使以P型雜質作爲雜劑，無法得到安定的具有 P型傳導之BP層。換言之，離子鍵結性大例如與砷化鎵 (GaAs : δ = 0·310)或氮化鎵（GaN : δ = 0·500 )等習知 III-V 族化合物半導體不同，僅單純地添加ρ型或η型雜質無法 達到安定控制如電阻率小的ρ型或η型磷化硼系半導體 層。 而且，添加Ρ型或η型雜質之原因，例如是否會影響硼 空孔之生成並不明確。因此，沒有揭示可控制抗區分地段 缺陷濃度之變化、使企求電阻率之ρ型或η型磷化硼系半 導體層安定、得到適合的ρ型或η型雜質。本發明由於有 鑑於克服上述習知技術的問題點，其主旨係提供一種離子 鍵結性小、雙鍵性強的I I I - V族化合物半導體，特別是以 磷化硼（ΒΡ)爲基材所成的η型或ρ型磷化硼系半導體層藉 由氣相成長方法製得時，就抗區分地段缺陷之相對濃度而 言添加η型或ρ型雜質，例如可安定製得精密控制的載體 濃度之η型或ρ型磷化硼系半導體層之技術方法。另外， 以提供一種利用具有企求電阻之η型或ρ型磷化硼系半導 體層構成的發光元件等之磷化硼系半導體元件爲目的。 換言之，本發明係提供在於單結晶基板上所形成具內部 存在有占有硼（Β)之空孔的磷（Ρ)、占有磷之空孔的硼、含 有硼與磷作爲構成元素之磷化硼（ΒΡ)系半導體層的磷化硼 578209 五、發明說明（4) 系半導體元件，具有下述（1)〜（4)項記載的特徵之磷化 硼系半導體元件。 (1) 其特徵爲含有高於占有硼之空孔的磷原子濃度之占 有磷之空孔的硼，且具有添加有第II族元素或第IV族元 素之P型雜質的p型磷化硼系化合物半導體層。 (2) 其特徵爲含有高於占有磷之空孔的硼原子濃度之占 有硼之空孔的磷，且具有添加有第IV族元素或第IV族元 素之η型雜質的η型磷化硼系化合物半導體層。 (3) 如上述（1)或（2)中記載的磷化硼系半導體元件，其 中具有含有高於占有硼之空孔的磷原子濃度之占有磷之空 孔的硼，且具有添加第II族元素或第IV族元素之ρ型雜 質的Ρ型磷化硼系化合物半導體層，及含有高於占有磷之 空孔的硼原子濃度之占有硼之空孔的磷，且具有添加有第 IV族元素之η型雜質的η型磷化硼系化合物半導體層兩 者。 (4)如上述（3)記載的磷化硼系半導體元件，其中作爲ρ 型雜質之第I I族元素爲至少一種鋅（Ζη )、鎘（Cd )及水銀 (Hg)、且作爲η型雜質添加的第IV族元素係爲錫（Sn)。 另外，本發明係提供一種爲形成構成磷化硼系半導體 元件使用的磷化硼系半導體層時，下述（5 )〜（1 2 )記載的 磷化硼系半導體層之製法。 (5 ) —種如上述（1 )記載的磷化硼系半導體元件的製法， 其特徵爲在基板溫度1000〜120(TC下、對第III族構成元 578209 五、發明說明（5) 素的原料而言第V族構成元素的原料之供應比例爲7 0〜 150之範圍內、且添加第η族元素或第iv族兀素之p型 雜質的原料、在單結晶基板上使p型磷化硼系半導體層氣 相成長。 (6 ) —種如上述（2 )記載的磷化硼系半導體元件的製法， 其特徵爲在基板溫度750〜1000 °C下、對第III族構成元 素的原料而言第V族構成元素的原料之供應比例爲7 0〜 150之範圍內、且添加第iv族元素或第VI族元素之η型 雜質的原料、在單結晶基板上使η型磷化硼系半導體層氣 相成長。 (7) —種如上述（3)或（4)記載的磷化硼系半導體元件的 製法，其特徵爲在基板溫度1 000〜1 2 0 0 °C下、對第III 族構成元素的原料而言第V族構成元素的原料之供應比例 爲70〜150之範圍內、且添加第π族元素之p型雜質的 原料、在單結晶基板上使p型磷化硼系半導體層氣相成 長。 (8 ) —種如上述（3 )或（4 )記載的磷化硼系半導體元件的 製法，其特徵爲在基板溫度7 5 0〜1 〇 〇 〇 °c下、對第π I族 構成兀素的原料而言第V族構成元素的原料之供應比例爲 70〜150之範圍內、且添加第iv族元素之n型雜質的原 料、在單結晶基板上使η型磷化硼系半導體層氣相成長。 (9 )如上述（5 )記載的磷化硼系半導體元件的製法，其 中在t又有形成棚聚合物（組成式RBx : R係表示第I I族或 五、發明說明（6) 第IV族元素、X係表示一般2〜12之正偶數）、添加第π 族或第IV族元素之原料、且使ρ型磷化硼系半導體層氣 相成長。 (1 0 )如上述（6 )記載的磷化硼系半導體元件的製法，其 中在沒有形成硼聚合物（組成式RBx : R係表示第τ丨族或 第IV族元素、X係表示一般2〜12之正偶數）、添加第η 族或第IV族元素之原料、且使η型磷化硼系半導體層氣 相成長。 (11)如上述（9)記載的磷化硼系半導體元件的製法，其 中加含有鋅（Ζη)、鎘（Cd )、水銀（Hg )、或錫（Sn)之原料以 使P型磷化硼系半導體層氣相成長。 (1 2 )如上述（1 0 )記載的磷化硼系半導體元件的製法， 其中添加含有錫（Sn)之原料以使n型磷化硼系半導體層氣 相成長。 此外，本發明爲 (13)如上述（1)〜（4)記載的磷化硼系半導體元件，其 中半導體元件係爲半導體發光元件（LED)。 【實施方式】 本發明之第1實施形態的磷化硼系半導體層，以通式 BotAlpGaYIn].a.p.YP1.6As6(0< 1 > β< 1 ' 0^γ< 1 ' 0 < α+β+γ€ 1、0S δ< 1)所示之磷化硼系半導體所構成。另 外，例如可由通式 BaAlpGaylnimPHfMCX 1、0$ β <1、0$γ<1、0<α+β + γ$1、0<δ<1)所示之含氮（Ν)之 五、發明說明（7) 磷化硼系半導體所構成。較佳者系構成元素數少、可簡單 構成的2元結晶或3元結晶所構成。例如單體磷化硼 (BP)、（ΒαΑ1ρΡ : 0< aS 1、α + β = 1)、磷化鋁•硼混晶 (BaGa5P : 0< 1、α+ δ=1)、或磷化硼·銦混晶（ΒαΙηι· αΡ : 0< 1 )等所構成。 本發明之Ρ型或η型磷化硼系半導體層，其特徵爲具有 故意在沒有添加雜質下、所謂的未摻雜狀態下硼空孔與磷 空孔之相對濃度關係。說明未摻雜之磷化硼單體（ΒΡ )單結 晶例時，其特徵爲占有硼空孔之磷原子、與占有磷空孔之 硼原子之量關係。於ΒΡ單結晶之理想構成結晶格子中， 占有硼空孔之磷（Ρ)係與占有格子位置之周圍磷（Ρ)原子鍵 結、形成Ρ-Ρ鍵。另外，占有磷空孔之硼（Ρ)係與占有格 子位置之周圍硼（Β )原子鍵結、形成Β - Β鍵。因此，占有 磷空孔之硼原子、與占有硼空孔之磷原子的相對關係爲Ρ-Ρ鍵與Β - Β鍵之量關係係爲已知。此等鍵結量與以bp單體 單結晶格子爲主所成的硼與磷之鍵（Β - Ρ鍵）相同，例如可 藉由核磁共振（NMR)分析法或拉曼（譯音）（Raman)分光分析 法等分析法調查。 本發明之P型磷化硼系半導體層，其特徵爲在未摻雜狀 態形成較硼空孔濃度高的磷空孔狀態、在該狀態下添加 (do pi ng)p型雜質、製得ρ型磷化硼系半導體層。在此硼 空孔之濃度大於磷空孔之濃度狀態下，會導致多量占有硼 空孔之磷或矽等施體成分生成。因此，僅單純地添加ρ型雜質 578209 五、發明說明（8) 時，例如無法簡單、安定地製得在室溫下之電阻率（比電 阻）爲0·1Ω· cm以下低電阻之p型磷化硼系半導體層。故 意添加的P型雜質，通常與以大於1〇19〜l〇2Dcm·3之高濃 度存在的硼空孔相關的施體（d ο η 〇 r )成分受到電氣補償 (compensation)作用之影響。然而，使與硼空孔相關的多 量施體磁法達到充分電氣補償，殘存作爲n型層、或例如 形成缺乏導電性之電阻率大於1〇2Ω的高電阻磷化硼系結 晶層等缺點。 爲使磷空孔以硼空孔以上存在時，以未摻雜狀態具有Ρ 型傳導性之磷化硼系半導體層回歸狀態下，所添加的Ρ型 雜質具有可有效作爲受體之作用。特別是具有Ρ型傳導性 時，可以少量Ρ型雜質作爲殘留施體成分予以電氣補償， 大部分Ρ型雜質可作爲受體運作。因此，在該狀態下藉由 增減Ρ型雜質之添加量，可安定製得具有電阻率經控制的 Ρ型磷化硼系半導體層之優點。同樣的優點，於同時添加 數種Ρ型雜質例如添加鎘（Cd )與鋅（Ζη )亦可得。於無法形 成與硼例如組成式RBX ( R係表示第11族元素、χ 一般爲2 〜12之正偶數）所示硼多聚物化合物之第η族元素可適合 利用作爲Ρ型雜質。第11族元素中更佳的ρ型雜質例如 鋅（Ζη)、鎘（Cd)及水銀（Hg)。而且，於磷化硼系半導體層 之成膜溫度中，可利用上述不易與硼形成硼多聚物、形成 兩性雜質之第IV族元素的碳（C )、矽（S i )或錫（Sn )。 爲製得P型111 - V族化合物半導體層時，習知常用的 -10- 578209 五、發明說明（9) 錶（Mg)(梦照 J. Appl. Phys·，58(8)(1985)、R31 〜R55 頁）、在小於1 050°C、或1150〜1 200°C之溫度下，由於例 如形成MgB4、或MgB6、MgB12等硼多聚物，故不適合作爲 P型雜質。爲形成硼多聚物時消耗多量硼原子，故會產生 多量硼空孔、且強迫占有硼空孔之磷（P )的抗區分地段缺 陷增量。因此，爲使施體成分增量，故會產生阻害安定形 成P型傳導層的情形。另外，鋅（Zn )、鎘（Cd)、或水銀（Hg ) 不會形成如硼與RBX之多聚物。因此，此等第11族元素 具有可抑制因 雜之硼空孔濃度增加的優點。換言之，由 於可迴避由占有硼空孔之磷所成的施體性抗區分地段缺陷 增量，且可發揮抑制背面密封套的施體濃度變化，故具有 使一定電阻率或載體濃度等之磷化硼系半導體導電體層安 定的貢獻。578209 V. Description of the invention (1) [Technical Field] The present invention relates to a technology for forming a boron phosphide-based compound semiconductor element by using a P-type or n-type conductivity or high resistance boron phosphide-based semiconductor layer. [Prior art] Since ancient times, a group III-V compound semiconductor has been known as boron phosphide (BP). (Refer to Terumoto Teramoto, "Semiconductor Device Theory" (March 30, 995, Peifeng Pavilion) Issue, p. 28)). Boron phosphide is a Phillips ionic bond (= δ) of 0.006. Alkali is almost all double-bond semiconductors (by Phillips, "Conclusion of Semiconductor Bonds" (refer to July 25, 1985, ) Yoshioka Bookstore Issue 3, page 51)). At the same time, boron phosphide is cubic-type zinc sphalerite (zinc-b 1 end) type crystal (refer to the above-mentioned "Semiconductor Device Theory", page 28), and hexagonal wurtzite such as gallium nitride (GaN). (Wii rtzite) -type semiconductor crystals with different valence electron bands (refer to co-authored by Ikuko Hideki and Ikuko Hideki, "Introduction to Basic Physical Properties of Compound Semiconductors") (September 10, 1991, issued by Peifeng Pavilion) , Pages 14-17). Therefore, boron phosphide, for example, has a basic feature that it is easier to produce a p-type conductive layer than high-fiber crystalline GaN having an ionic bond degree (δ) of 0.50 (refer to the "Semiconductor Bond Conclusion", page 51) . According to this feature, a conventional p-type boron phosphide semiconductor layer such as a laser diode (LD) is used as a contact layer provided with an electrode (see Japanese Patent Application Laid-Open No. 10-242 5 67). In addition, it is revealed that an LD is formed by a p-type boron phosphide layer as a buffer on a gallium arsenide (GaP), silicon carbide (S i C), or GaN single crystal substrate. 578209 5. Description of the invention (2) Layered structure constituted by LD Or light-emitting diode (LED) technology. In addition, a conventional example in which a mixed crystal of boron phosphide to which a p-type impurity is added and aluminum nitride gallium (AlxGa) _xN · · 〇 'X $ 1) is used as a light emitting layer to constitute a light emitting device (see JP 2-27) 5 682). In the conventional technology, the p-type boron phosphide layer is formed by forming a p-type impurity by an organic metal thermal decomposition vapor phase growth method (M0CVD) such as magnesium (Mg) or zinc (Zn) (refer to US Patent No. 6,069,021). However, the so-called undoped boron phosphide without intentional addition of impurities is said to have the possibility of having a vacancy of the boron (see Zhuangye Kefang, "Super LS I Semiconductor Technology of the Age 100 Episode III] "(share) Ohm Corporation, issued on April 1, Showa," Electronic Journal of Electronics ", Volume 27, page 4 (April Showa 57) Academic Library 18, 86 ~ 87). In other words, the possibility of phosphorus atoms occupying the regular lattice positions of boron was revealed. In addition, the possibility of boron existing in the pores of phosphorus was revealed. The phosphorus system that occupies the regular lattice position of boron phosphide of cubic sphalerite has a donor function (see "Semiconductor Technology in the Ultra-LSI Age [III]", pages 86 to 87). On the other hand, the boron system possessing the regular lattice has a receptor function (refer to the above-mentioned "Semiconductor Technology in the Age of LS I [III]", pages 86 to 87). [Summary of the Invention] As described above, the possibility that the boron phosphide layer contains an anti-distance section (8111 s s! Te) is revealed (refer to the co-author Ikuko Hideki, Ikuko Hideki, "Introduction to Basic Physical Properties of Compound Semiconductors") , (First release on September 10, 1991), 1 4 1 pages). Defects in the anti-distance section are in large amount because of the defects related to boron (B) and pity (P) of the constituent elements of the invention (3). Therefore, for example, in the state of phosphorus having a large number of space dots occupying boron as donors, even if a P-type impurity is used as a dopant, a stable BP layer having P-type conduction cannot be obtained. In other words, the ionic bondability is large, unlike conventional III-V compound semiconductors such as gallium arsenide (GaAs: δ = 0.310) or gallium nitride (GaN: δ = 0.500), and only ρ is simply added. Type or n-type impurities cannot achieve stable control such as a p-type or n-type boron phosphide-based semiconductor layer having a small resistivity. In addition, the reason for the addition of P-type or η-type impurities, for example, whether it will affect the generation of boron pores is not clear. Therefore, it is not disclosed that the change in the concentration of defects in the anti-distance section can be controlled to stabilize the p-type or n-type boron phosphide-based semiconductor layer for which the resistivity is sought, and to obtain suitable p-type or n-type impurities. In view of overcoming the problems of the conventional technology, the present invention aims to provide a III-V compound semiconductor with low ionic bonding and strong double bonding, especially based on boron phosphide (BP) as a substrate. When the formed η-type or ρ-type boron phosphide-based semiconductor layer is prepared by a vapor phase growth method, η-type or ρ-type impurities are added in terms of the relative concentration of the defects that are resistant to distinguishing the area, for example, a carrier that can be precisely controlled by installation A technical method for the concentration of n-type or p-type boron phosphide-based semiconductor layers. Another object is to provide a boron phosphide-based semiconductor element such as a light-emitting element including an n-type or p-type boron phosphide-based semiconductor layer having a desired resistance. In other words, the present invention provides boron phosphide (P) with voids occupying boron (B), boron occupying voids formed on a single crystal substrate, and boron phosphide containing boron and phosphorus as constituent elements. Boron Phosphide of (BP) -based semiconductor layer 578209 5. Description of the Invention (4) A semiconductor device having a boron phosphide-based semiconductor device having the characteristics described in the following items (1) to (4). (1) P-type boron phosphide characterized by boron containing pores containing phosphorus having a higher concentration of phosphorus atoms than pores occupying boron, and having P-type impurities added to a Group II element or a Group IV element Is a compound semiconductor layer. (2) It is characterized by η-type boron phosphide containing pores occupying boron containing a higher concentration of boron atoms than pores occupying phosphorus, and having η-type impurities added to a Group IV element or a Group IV element Is a compound semiconductor layer. (3) The boron phosphide-based semiconductor device as described in (1) or (2) above, which has boron containing porosity containing porosity having a higher concentration of phosphorus atoms than the porosity of porosity occupied by boron, and has an added second P-type boron phosphide-based compound semiconductor layer of p-type impurity of a group element or a group IV element, and phosphorus containing boron-occupied pores having a higher concentration of boron atoms than the porosity of occluded phosphorous, and having an added IV Both an n-type boron phosphide-based compound semiconductor layer of an n-type impurity of a group element. (4) The boron phosphide-based semiconductor device according to the above (3), wherein the Group II element as the ρ-type impurity is at least one of zinc (Zη), cadmium (Cd), and mercury (Hg), and as the η-type impurity The added Group IV element is tin (Sn). In addition, the present invention provides a method for producing a boron phosphide-based semiconductor layer described in the following (5) to (1 2) when forming a boron phosphide-based semiconductor layer used to constitute a boron phosphide-based semiconductor device. (5) A method for producing a boron phosphide-based semiconductor device as described in the above (1), characterized in that the substrate temperature is 1000 to 120 (TC, for group III constituent element 578209) V. Description of the invention (5) In terms of raw materials, the supply ratio of the raw materials of the group V constituent elements is within a range of 70 to 150, and the raw materials to which p-type impurities of a group n element or a group iv element are added, and p-type phosphorus is made on a single crystal substrate. The boron-based semiconductor layer is vapor-grown. (6) A method for producing a boron phosphide-based semiconductor device as described in (2) above, which is characterized in that the group III constituent elements are formed at a substrate temperature of 750 to 1000 ° C. In terms of raw materials, the supply ratio of the raw materials of the group V constituent elements is within a range of 70 to 150, and the raw materials to which the n-type impurities of the group iv element or the group VI element are added, and the n-type phosphating is performed on the single crystal substrate. The boron-based semiconductor layer is vapor-grown. (7) A method for producing a boron phosphide-based semiconductor device as described in (3) or (4) above, which is characterized in that the substrate temperature is 1,000 to 120 ° C, For Group III constituents, the supply ratio of Group V constituents is 70-150. A raw material in which a p-type impurity of a group π element is added, and a p-type boron phosphide-based semiconductor layer is vapor-grown on a single crystal substrate. (8) A species as described in (3) or (4) above The method for producing a boron phosphide-based semiconductor device is characterized in that, at a substrate temperature of 7500 to 1000 ° C, the supply ratio of the raw material of the group V constituent element to the raw material of the group π I constituent element is In the range of 70 to 150, a raw material to which an n-type impurity of a Group iv element is added, a n-type boron phosphide-based semiconductor layer is vapor-grown on a single crystal substrate. (9) Phosphating according to the above (5) A method for manufacturing boron-based semiconductor devices, in which a polymer is formed at t (composition formula RBx: R represents Group II or V. Description of the invention (6) Group IV elements, X represents general positive and even numbers from 2 to 12. ), Adding a raw material of a group π or a group IV element, and vapor-phase growing the p-type boron phosphide-based semiconductor layer. (1 0) The method for producing a boron phosphide-based semiconductor device according to (6) above, wherein Boron polymer is not formed (composition formula RBx: R represents group τ 丨 or group IV elements, X represents general 2 Positive and even number of ~ 12), adding a raw material of a group η or a group IV element, and growing the η-type boron phosphide-based semiconductor layer in a vapor phase. (11) The boron phosphide-based semiconductor device according to (9) above A production method in which a raw material containing zinc (Zη), cadmium (Cd), mercury (Hg), or tin (Sn) is added to vapor-phase grow a P-type boron phosphide-based semiconductor layer. (1 2) As described above (1 0 The method for producing a boron phosphide-based semiconductor device according to), wherein a raw material containing tin (Sn) is added to vapor-phase grow the n-type boron phosphide-based semiconductor layer. Further, the present invention is (13) the boron phosphide-based semiconductor element according to (1) to (4) above, wherein the semiconductor element is a semiconductor light-emitting element (LED). [Embodiment] The boron phosphide-based semiconductor layer according to the first embodiment of the present invention has the general formula BotAlpGaYIn] .apYP1.6As6 (0 < 1 > β < 1 '0 ^ γ < 1' 0 < α + β + γ € 1, 0S δ < 1) is composed of a boron phosphide-based semiconductor. In addition, for example, the formula (5) of nitrogen-containing (N) shown by the general formula BaAlpGaylnimPHfMCX 1, 0 $ β < 1, 0 $ γ < 1, 0 < α + β + γ $ 1, 0 < δ < 1), invention description (7) It is made of boron phosphide semiconductor. The more preferable one is a binary crystal or a ternary crystal which can be easily constructed with a small number of constituent elements. For example, monomer boron phosphide (BP), (BαΑ1ρΡ: 0 < aS 1, α + β = 1), aluminum phosphide-boron mixed crystal (BaGa5P: 0 < 1, α + δ = 1), or boron phosphide -Indium mixed crystal (BαΙηι · αP: 0 < 1). The P-type or η-type boron phosphide-based semiconductor layer of the present invention is characterized by having a relative concentration relationship between boron pores and phosphorus pores in a so-called undoped state deliberately without the addition of impurities. When explaining an example of a single crystal of undoped boron phosphide monomer (BP), it is characterized by the relationship between the amount of phosphorus atoms occupying boron pores and the amount of boron atoms occupying phosphorus pores. In the ideal crystal lattice of BP single crystals, the phosphorus (P) occupying the pores of the boron is bonded with the phosphorus (P) atoms occupying the positions of the lattice to form a P-P bond. In addition, the boron (P) occupying the pores of the phosphorus is bonded to the surrounding boron (B) atoms occupying the lattice site to form a B-B bond. Therefore, the relative relationship between the boron atoms occupying the phosphorus pores and the phosphorus atoms occupying the pores is known as the amount relationship between the P-P bond and the B-B bond. The amount of these bonds is the same as the boron-phosphorus bond (B-P bond) formed by the bp monomer single crystal lattice. For example, it can be analyzed by nuclear magnetic resonance (NMR) analysis or Raman (Raman) ) Investigate analytical methods such as spectroscopic analysis. The P-type boron phosphide-based semiconductor layer of the present invention is characterized in that a phosphorus pore state with a higher concentration of boron pores is formed in an undoped state, and (do pi ng) p-type impurities are added in this state to obtain ρ Type boron phosphide-based semiconductor layer. In this state where the concentration of boron pores is greater than the concentration of phosphorus pores, a large amount of donor components such as phosphorus or silicon occupying boron pores will be generated. Therefore, only the p-type impurity 578209 is simply added. 5. In the description of the invention (8), for example, a p-type low-resistance with a resistivity (specific resistance) at room temperature of less than 0 · 1Ω · cm cannot be simply and stably prepared. Boron phosphide-based semiconductor layer. The intentional addition of P-type impurities, usually the constituents of the donor (d ο η ο r) associated with the boron pores present at a high concentration of more than 1019 to 10 Dcm · 3, are affected by the effect of electrical compensation. However, a large amount of donor magnetization methods related to boron pores have been achieved to fully compensate electrical, and remain as an n-type layer, or for example, a high-resistance boron phosphide-based crystalline layer having a resistivity of more than 10? That lacks conductivity. When the phosphorus pores exist above the boron pores, the added P-type impurities can effectively function as acceptors in the return state of the boron phosphide-based semiconductor layer having P-type conductivity in an undoped state. Especially with P-type conductivity, a small amount of P-type impurities can be used as a residual donor component for electrical compensation, and most P-type impurities can operate as acceptors. Therefore, by increasing or decreasing the amount of P-type impurities added in this state, it is possible to customize the P-type boron phosphide-based semiconductor layer with controlled resistivity. The same advantage can also be obtained by adding several P-type impurities such as cadmium (Cd) and zinc (Zη) simultaneously. Group η elements of a boron polymer compound that cannot be formed with boron, for example, a composition formula RBX (where R is a Group 11 element, and χ is generally a positive even number of 2 to 12) can be suitably used as a P-type impurity. More preferable p-type impurities in the Group 11 element are zinc (Zη), cadmium (Cd), and mercury (Hg). In addition, at the film formation temperature of the boron phosphide-based semiconductor layer, the carbon (C), silicon (S i), or tin (Sn) of the Group IV element that does not easily form a boron polymer with boron and form an amphoteric impurity can be used. ). In order to obtain P-type 111-V group compound semiconductor layers, -10- 578209 is commonly used. V. Description of the invention (9) Table (Mg) (Meng Zhao J. Appl. Phys ·, 58 (8) (1985) , Pages R31 to R55), at temperatures lower than 1 050 ° C or 1150 to 1 200 ° C, for example, it forms MgB4, MgB6, MgB12 and other boron polymers, so it is not suitable as a P-type impurity. In order to form a boron polymer, a large amount of boron atoms are consumed, so a large amount of boron pores are generated, and the increase in defect-resistant section of phosphorus (P) forcing the boron pores to be discriminated is increased. Therefore, in order to increase the donor composition, there is a case where the formation of a P-type conductive layer is hindered. In addition, zinc (Zn), cadmium (Cd), or mercury (Hg) does not form a polymer such as boron and RBX. Therefore, these Group 11 elements have the advantage of suppressing an increase in the concentration of vacant pores due to impurities. In other words, since it is possible to avoid the increase in the defect of the donor-resistant anti-distortion section made of phosphorus that occupies boron pores, and to suppress the change in the donor concentration of the back seal, it has a certain resistivity or carrier concentration, etc. Contribution of stability of boron-based semiconductor conductor layer.
在未摻雜狀態下具有P型傳導性、即占有磷空孔之硼 原子濃度在占有硼空孔之磷濃度以上時，另摻雜作爲p型 雜質之鋅（Zn )時磷化硼系半導體層之載體濃度的安定性如 第3圖所示。如第3圖所例示係爲溫度爲1050°C時使下述 V /111比例約設疋爲1 〇 〇，以有機金屬熱分解氣相成長 (MOCVD )法成膜的單體p型磷化硼（BP)半導體層之載體濃 度。使鋅（Zn )之摻雜量一定時，所得載體濃度以3 . 2 X 1019 cm_3作爲平均値之±4 .5%係安定。電阻率之變動異大 約在該範圍內安定。另外，如第3圖之對比所示，在故意 沒有添加鋅' 未摻雜（undope)狀態下載體濃度爲2.8X 578209 五、發明說明（1〇) 1019cnr3±50.7%、分布範圍廣，不安定。換言之，有關硼 或磷之空孔的抗區分地段之相對濃度僅以單純規定的狀態 下之技術法，無法達成安定製得企求載體濃度或電阻率之 磷化硼係半導體層，係可明瞭。適合磷化硼（BP)成膜時之 7 5 0°C〜1 200°C下添加構成MgB4等硼多聚物之鎂（Mg)作爲 p型雜質時，藉由使伴隨多聚物形成時產生的佔有硼空孔 之磷的抗區分地段增量，與上述鋅（Zn)摻雜不同、無法 達成製得載體濃度或電阻率安定的P型磷化硼係半導體 層。使Mg之摻雜量增加時，會引起由占有較多量的硼空 孔之磷所成摻雜成分增加，無法製得P型傳導層、形成高 電阻層。 另外，在未摻雜狀態下已經存在有磷空孔之濃度在硼 空孔之濃度以上的狀態時，即受體之占有磷空孔的硼原子 多量存在的狀態下，即使添加η型雜質、會有在沒有電氣 補償下製得殘留有受體成分之Ρ型層的缺點。而且，僅形 成高電阻層。如本發明所揭示，創造在未摻雜狀態下硼空 孔之濃度在磷空孔之濃度以上存在的狀態時，添加的η型 雜質部分形成受體與施體/一對受體被消耗者、大部分η 型雜質可作爲電氣活性施體運作。因此，在該狀態下藉由 增減η型雜質之添加量，可安定製得具有電阻率經控制的 η型磷化硼系半導體層之優點。Ν型雜質例如第I V族矽 (Si)或錫（Sn)、及硒（Se)、硫（S)、碲（Te)等之第VI族元 素。另外，數種η型雜質例如添加錫（Sn )與矽（S i )倂用、 -12- 五、發明說明（11) 亦具有相同的優點。 特別是無法形成錫（Sn)表示SnBx(X係表示硼之組成 比、X —般爲2〜12之正偶數）等之硼多聚物。因此，因 摻雜而使硼空孔之濃度增加，強迫由占有硼空孔之磷所成 施體的抗區分地段缺陷增量。因此，由於可迴避因摻雜之 背面密封套的施體濃度變化，故具有使一定電阻率或載體 濃度等之磷化硼系半導體導電體層安定的貢獻。錫（Sn)之 添加源例如四乙基錫（（C2H5)4Sn)等之有機錫化合物。 磷化硼系半導體層例如矽單結晶（矽）、磷化鎵（GaP)、 砷化鎵（GaAs)、碳化矽（SiC)、或磷化硼（BP)(參照（1)J. Electrochem. Soc·， 120(1973)、ρ·ρ· 802〜806、及（2) 美國專利5,042,043號公報）等之單結晶作爲基板、例如 藉由氣相成長法予以成膜。製得磷化硼系半導體層之氣相 成長法有利用三乙基硼（（C2H5)3B)/膦（PH3)/氫（H2)成長反 應系之 M0CVD 法（Inst. Phys. Conf. Ser.，No. 129(IOP Publishing Ltd·，1993)、157 〜162 頁）。另外，例如有 三氯化硼（BC13)/三氯化磷（PC13)/H2反應系鹵素（halogen) 氣相成長法、及二硼烷（B2H6)/PH3/H2反應系鹵化物 (Hydride)氣相成長法。而且，可例如分子線外延成長法 (參照 J. Solid State Chei, 133(1997)、269 〜272 頁）。 形成磷化硼結晶層時以約在7 50〜1 200t之溫度範圍爲 宜。若大於約120CTC之高溫時，例如會產生B13P2之多聚 -13- 578209 五、發明說明（12 ) 物（J. Am. Ceram. Soc·， 47(1)(1964) 、 44〜46 頁）、無 法製得組成均質的磷化硼系半導體層。以三乙基硼 ((C2H5)3B)/膦（PH3)/氫（H2)成長反應系之M0CVD法，製得 在未手段雜狀態下占有硼空孔之磷原子、或有關硼空孔之 手段雜成分的濃度較有關磷空孔之受體濃度高的磷化硼系 化合物半導體層時，成膜溫度（基板溫度）以750〜100(rc 爲宜。另外，在未摻雜狀態下，占有磷空孔之硼原子、或 有關磷空孔之摻雜成分的濃度，較有關硼空孔之受體濃度 高的磷化硼系化合物半導體層時，成膜溫度（基板溫度）以 1 000 〜1 200°C 爲宜。 在上述適合的溫度範圍內，使磷化硼系半導體層成膜 時，若V/1 I I供應比例小於70時，會形成基板表面上混 在各種結晶面之多結晶層，變成製得單結晶層之障礙。多 結晶層，例如在結晶粒界中產生轉位情形、或產生因粒界 存在而使載體之移動度降低等之結晶學上活電學品質惡化 的情形，係無法構成高性能磷化硼系化合物半導體元件。 若V/ I 11供應比例爲70〜120之範圍內時，構成磷化硼系 化合物半導體層之結晶面劃一；而若V/1 11供應比例大於 120時，磷等之V族元素供應過多、會產生含磷之結晶 物、且形成欠缺表面平滑性之磷化硼系半導體層，故不爲 所希望。 本發明之η型或p型磷化硼系半導體層，由於電阻率 或載體濃度安定、可利用於製作特性安定的磷化硼系半導P-type conductivity in an undoped state, that is, when the concentration of boron atoms occupying phosphorus pores is higher than the concentration of phosphorus occupying boron pores, a boron phosphide-based semiconductor is additionally doped with zinc (Zn) as a p-type impurity. The stability of the carrier concentration of the layer is shown in FIG. 3. As exemplified in Figure 3, the p-type phosphorylation of the monomer formed by the organic metal thermal decomposition vapor phase growth (MOCVD) method is performed at a temperature of 1050 ° C and the following V / 111 ratio is set to about 100. The carrier concentration of the boron (BP) semiconductor layer. When the doping amount of zinc (Zn) is made constant, the carrier concentration obtained is 3.2 × 1019 cm_3, which is an average of ± 4.5%. The variation in resistivity is approximately stable within this range. In addition, as shown in the comparison of FIG. 3, the concentration of the download body in the undope state without intentional addition of zinc was 2.8X 578209. 5. Description of the invention (10) 1019cnr3 ± 50.7%, wide distribution range, unstable . In other words, it is clear that the relative concentration of the anti-distortion section of the pores of boron or phosphorus can only be achieved by a technical method under a simple prescribed state, and a boron phosphide-based semiconductor layer that can be customized to obtain the carrier concentration or resistivity can be achieved. Suitable for the formation of boron phosphide (BP) film at 750 ° C ~ 1 200 ° C when magnesium (Mg) constituting a boron polymer such as MgB4 is added as a p-type impurity. The increase in the anti-distortion area of the phosphorus occupying boron pores is different from the above-mentioned zinc (Zn) doping, and a P-type boron phosphide-based semiconductor layer with stable carrier concentration or resistivity cannot be obtained. Increasing the doping amount of Mg will cause an increase in the doping composition of phosphorus that occupies a large amount of boron pores, making it impossible to obtain a P-type conductive layer and form a high-resistance layer. In addition, in a state where the concentration of phosphorus pores is higher than the concentration of boron pores in an undoped state, that is, in a state where a large number of boron atoms occupying phosphorus pores are present in the acceptor, even if η-type impurities are added, There is a disadvantage in that a P-type layer with a residual acceptor component is produced without electrical compensation. Moreover, only a high-resistance layer is formed. As disclosed in the present invention, when a state in which the concentration of boron pores exists above the concentration of phosphorus pores in an undoped state is created, the added n-type impurity part forms an acceptor and a donor / a pair of acceptors to be consumed Most η-type impurities can operate as electrically active donors. Therefore, in this state, by increasing or decreasing the addition amount of the η-type impurity, the η-type boron phosphide-based semiconductor layer with controlled resistivity can be customized. The N-type impurities are, for example, Group I V silicon (Si) or tin (Sn), and Group VI elements such as selenium (Se), sulfur (S), tellurium (Te), and the like. In addition, several types of n-type impurities, such as the addition of tin (Sn) and silicon (Si), are used. -12- 5. Invention Description (11) also has the same advantages. In particular, boron polymers such as tin (Sn) representing SnBx (X is a composition ratio of boron, and X is generally a positive and even number of 2 to 12) cannot be formed. Therefore, the concentration of boron vacancies is increased due to doping, forcing the increase of defects in the anti-distinguishable section of the donor formed by phosphorus occupying the boron pores. Therefore, it is possible to avoid the change in the donor concentration of the back-sealing sleeve due to the doping, so that it contributes to the stabilization of the boron phosphide-based semiconductor conductor layer with a certain resistivity or carrier concentration. An addition source of tin (Sn) is an organic tin compound such as tetraethyltin ((C2H5) 4Sn). Boron phosphide-based semiconductor layers such as silicon single crystal (silicon), gallium phosphide (GaP), gallium arsenide (GaAs), silicon carbide (SiC), or boron phosphide (BP) (see (1) J. Electrochem. Single crystals such as Soc ·, 120 (1973), ρ · ρ · 802 to 806, and (2) U.S. Patent No. 5,042,043) are used as substrates, for example, formed by a vapor phase growth method. A vapor phase growth method for obtaining a boron phosphide-based semiconductor layer is a MOCVD method (Inst. Phys. Conf. Ser.) Using a triethyl boron ((C2H5) 3B) / phosphine (PH3) / hydrogen (H2) growth reaction system. , No. 129 (IOP Publishing Ltd., 1993), pages 157 to 162). In addition, there are, for example, boron trichloride (BC13) / phosphorus trichloride (PC13) / H2 reaction type halogen vapor phase growth method, and diborane (B2H6) / PH3 / H2 reaction type halogen compound gas. Phase growth method. Further, for example, the molecular wire epitaxial growth method can be used (see J. Solid State Chei, 133 (1997), pages 269 to 272). The boron phosphide crystal layer is preferably formed in a temperature range of about 7 50 to 1 200 t. If it is higher than about 120CTC, for example, a polymer of B13P2-13- 578209 will be produced. 5. Description of the invention (12) (J. Am. Ceram. Soc ·, 47 (1) (1964), pages 44 ~ 46) It is impossible to obtain a boron phosphide-based semiconductor layer having a homogeneous composition. Using the MOCVD method of the triethyl boron ((C2H5) 3B) / phosphine (PH3) / hydrogen (H2) growth reaction system, the phosphorus atoms occupying the pores of the boron in the unresolved state or the related boron pores In the case of a boron phosphide-based compound semiconductor layer having a higher impurity concentration than the acceptor concentration of the phosphorus pores, the film formation temperature (substrate temperature) is preferably 750 to 100 (rc. In addition, in an undoped state, When the concentration of the boron atom occupying the phosphorus pores or the doping component of the phosphorus pores is higher than that of the boron phosphide compound semiconductor layer having the acceptor concentration of the pores, the film formation temperature (substrate temperature) is 1 000 It is preferable to be ~ 1 200 ° C. When the boron phosphide-based semiconductor layer is formed in the above-mentioned suitable temperature range, if the V / 1 II supply ratio is less than 70, polycrystals mixed on various crystal surfaces on the substrate surface will be formed. The layer becomes an obstacle to the production of a single crystalline layer. For a polycrystalline layer, for example, a translocation occurs in the crystal grain boundary, or a decrease in the mobility of the carrier due to the existence of the grain boundary causes a deterioration in the crystallographic bioelectrical quality. , Can not constitute a high performance boron phosphide compound semiconductor If the supply ratio of V / I 11 is within the range of 70 to 120, the crystal planes constituting the boron phosphide-based compound semiconductor layer are uniform; and if the supply ratio of V / 1 11 is greater than 120, the supply of group V elements such as phosphorus is supplied. Too much, it will generate phosphorus-containing crystals and form a boron phosphide-based semiconductor layer that lacks surface smoothness, which is not desirable. The n-type or p-type boron phosphide-based semiconductor layer of the present invention has a resistivity or a carrier because Stable concentration, can be used to make stable boron phosphide semiconductors with stable characteristics
-14- 578209 五、發明說明（13 ) 體元件。例如，利用本發明之η型及p型磷化硼系半導體 層兩者，可構成具備ρη接合構構體特性之安定磷化硼系 半導體二極管等。例如於LED或LD中，利用作爲電阻率 安定的p型及η型磷化硼系半導體層夾住發光層之覆蓋層 時，可構成順方向電壓（Vf)或閥値電壓（Vth)安定的ριι接 合型雙雜（DH)構造之LED或LD。發光層例如可由含有氮化 鎵·銦混晶（G a x I η !. x N ·· 0 S X S 1 )或氮（N )與氮以外之磷（p ) 等第V族元素爲構成元素的氮化鎵混晶（GaPyNn : 0< Y< 1)等構成。特別是構成覆蓋層之憐化硼系半導體層與具有 不齊（m i s m a t c h )少的格子面間隔之組成G a χ I η ,. χ混晶（0 S XS 1)或GaPyIVy混晶（0<Υ<1)等之發光層構成時，可構 成具有優異亮度特性的發光元件。 於磷化硼系化合物半導體中，以大於占有硼空孔之磷 原子濃度的濃度存在之占有磷空孔之硼，可形成具有Ρ型 傳導之背面密封套，由於添加ρ型雜質、可得安定的ρ型 磷化硼系化合物半導體、且具有藉由控制ρ型雜質之添加 量可製得具有電阻率、載體濃度經控制的Ρ型磷化硼系化 合物半導體層之作用。 於磷化硼系化合物半導體中，以大於占有磷空？ L之硕月 原子濃度的濃度存在之占有硼空孔之磷，可形成具有η型 傳導之背面密封套，由於添加η型雜質、可得安定的η型 磷化硼系化合物半導體、且具有藉由控制η型雜質& $加· 量可製得具有電阻率、載體濃度經控制的η型磷化_系化 -15- 578209 五、發明說明（彳4) 合物半導體層之作用。 【實施例】 本發明係利用在矽單結晶（矽）基板上所設的p型及η 型磷化硼（BP)半導體層、構成磷化硼系半導體發光元件 (LED)爲例予以具體說明。 本實施例之LED 1 B之截面模式圖，如第1圖所示。在 單結晶基板1 0 1係使用以（1 1 1 )結晶面爲表面、添加有硼 (B)之P型矽單結晶。在基板101表面上藉由由三乙基硼 ((C2H5)B3)/膦（PH3)/氫（H2)系之常壓 MOCVD 法、在 1 050°C 下形成由摻雜鋅的（111 ) - p型磷化硼（BP)所成下部覆蓋層 102。而且，形成時將V/III比例（=PH3/(C2H5)3B)之供應 約設定爲1 1 5。由利用雷射拉曼分光法等之分析可知，以 同溫度及同V/III比例成長的未摻雜（undope)之BP層內 占有磷空孔的硼濃度大於占有硼空孔之磷濃度，其量約大 於ixi019cm·3。鋅之摻雜源係使用二甲基鋅（（CH3)2Zn)-氫 混合氣體（體積混合例約=1 〇 〇 v ο 1 · p p m )，下部覆蓋層1 0 2 之載體濃度約爲1 X l〇19cm·3。二甲基鋅之供應量爲每分鐘 2X 10_6莫耳（mol )。另外，層厚約爲400nm之下部覆蓋層 在室溫下由禁止帶寬度約爲3eV之磷化硼（BP)所構成。 立方晶閃鋅礦結晶型（Sphareli te)之BP下部覆蓋層 1 02上形成由六方晶纖鋅礦結晶型^型氮化鎵•銦所成的 發光層103。發光層之Q6層係藉由三甲基鎵 ((CH3)3Ga)/二甲基銦（（CH3)3In) /胺（NH3)/·氣（Ar) /氫（H2) -16- 578209 五、發明說明（15) 系之常壓MOCVD氣相成長法、在850°C下成長。發光層 103之載體濃度約爲2 X 1018cm·3，層厚約爲600nm。使波 長爲3 25nm之氨氣（He)-鎘（Cd)雷射光入射時之發光層103 所成的光阻發光（PL)光譜，如第2圖所示。PL光之中心波 長約爲427 . 5nm。而且，雷射光之入射強度約爲0 · 2mW時 PL強度約爲7 . OmV，藍紫色PL光譜之半値寬約爲 3 7 8.6meV 〇 在發光層103上係利用磷化硼（BP)層成膜時所利用的上 述常壓MOCVD法，在850°C下形成由錫（Zn)摻雜η型BP 層所成上部覆蓋層1 04。另外，形成時V/ I I I比例 (=PH3/(C2H5)3B供應比例）約設定爲100。利用雷射拉曼分 光法分析時，在同溫度及同V/ I I I比例成長的未摻雜 (un dope)之BP層內占有硼空孔之磷濃度大於占有磷空孔 之硼濃度，其量約爲3 X 1019cm·3。錫之摻雜源係使用四乙 基錫。四乙基錫之供應量每分鐘爲1 .0 X 10·6莫耳（mol ), 上部覆蓋層104之載體濃度調整爲4X10 19cm_3。上部覆蓋 層104之η型BP層在室溫下禁止帶寬係由吸收係數之波 長（光子能量）相關性求得、約爲3eV。上部覆蓋層1〇4之 層厚約爲4 0 0 n m。 在單結晶基板101、下部覆蓋層102、發光層1〇3、上 部覆蓋層104所成的積層構造體1Α之上部覆蓋層104中 央配置由金•鍺（Au· Ge)合金所成的圓形（直徑=ΐι〇μιτ1)2 歐姆性η型表面電極1 0 5。而且，在大約ρ型矽單結晶基 -17- 578209 五、發明說明（16 ) 板1 0 1裡面之全面設置由鋁（A 1 )所成的歐姆性p型裏面電 極106，形成pn接合型雙雜黏合構造之LED1B。在兩電極 105、106上使電極材料被熔後，在氮氣氣流中、42(TC 下、施予合金化（alloying)熱處理。 在η-側面上（n-side up)型LED1B上使20mA順方向 (f 〇 r w a r d )電流流通，可得下述（a )〜（d )項記載之特性。 (a) 發光中心波長：約430nm (b) 亮度：0.8cd (c) 順方向電壓：3V (d) 逆方向電壓：8V(逆方向電流=10μΑ) 特別是使夾住發光層之下部及上部覆蓋層102、105由高 載體濃度η型或ρ型磷化硼層所構成，故可提供順方向發 出電壓低的藍紫帶光之LED。而且，特別以覆蓋層102、 105透過發光、具有充分廣泛的禁止帶寬度之由單體磷化 硼構成，故可提供高亮度的藍紫色LED。 【發明效果】 本發明係於具備有矽等之單結晶基板上形成的存在有 占有硼空孔之磷、與占有磷空孔之硼雙方、且含有以硼與 磷爲構成元素之磷化硼系半導體層之磷化硼系半導體元件 中，使具有ρ型傳導之磷化硼系半導體層氣相成長時，由 於在未摻雜狀態下具有含有占有硼之空孔的磷原子濃度以 上之占有磷之空孔的硼，且具有添加有第II族元素或第 IV族元素之ρ型雜質、可製得ρ型磷化硼系化合物半導體 -18- 578209 五、發明說明（17) 層，故利用電阻率或載體濃度安定的磷化硼系半導體層， 可提供例如電氣特性優異的磷化硼系半導體元件。 由於在未摻雜狀態下，含有占有磷之空孔的硼原子濃度 以上之占有硼之空孔的磷，且具有添加有第IV族元素或 第VI族元素之η型雜質、型成η型磷化硼系化合物半導 體層，故利用電阻率或載體濃度安定的磷化硼系半導體層， 可提供例如電氣特性優異的磷化硼系半導體元件。 特別是本發明由於在使磷化硼系半導體層氣相成長的 適合溫度範圍中，藉由添加不易與硼形成多聚物之元素作 爲η型或ρ型雜質，製得η型或ρ型傳導性磷化硼系半導 體層，故可抑制伴隨硼多聚物形成產生的引起空孔濃度變 動之電阻率不安定性、例如可使高載體濃度之磷化硼系半 導體層安定，且利用該高載體濃度之導電層、可達到製得 例如順方向電壓低的省電型磷化硼系半導體發光元件之效 果。 本發明由於在單結晶基板上、溫度1 〇 〇 〇〜1 2 〇 0 °c下、 封弟I I I族構成兀素的原料而言，第\/族構成元素的原料 之供應比例爲70〜150之範圍內、且添加第π族元素或 第IV族元素之ρ型雜質、形成ρ型磷化硼系半導體層， 故可達成減低爲電氣補償殘留的施體成分所耗費的受體量， 所以可以高載體濃度安定形成低電阻率之ρ型磷化硼系半 導體層之效果。 另外，本發明由於在單結晶基板上、溫度75〇〜1〇〇〇 -19- 578209 五、發明說明（18) °C下、對第III族構成元素的原料而言第v族構成元素的 原料之供應比例爲70〜150之範圍內、且添加第IV族元 素之η型雜質、形成η型磷化硼系半導體層，故可達成減 低爲電氣補償殘留的受體成分所耗費的η型雜質量、以高 載體濃度安定形成低電阻率之ρ型磷化硼系半導體層之效 果。 【圖式簡單說明】 【第1圖】 係爲本發明實施例之LED截面模式圖。 【第2圖】 係爲本發明實施例中LED之發光層的PL光譜。 【第3圖】 係爲摻雜鋅時與未摻雜時磷化硼系半導體層之載體 濃度的安定性圖。 【主要部分之代表符號】 1 A…積層構造體 IB··· LED 1 0 1…單結晶基板 102…下部覆蓋層 103…發光層 1 04…上部覆蓋層 105…η型裏面電極 106…ρ型裏面電極 -20--14- 578209 V. Description of the invention (13) Body element. For example, by using both the η-type and p-type boron phosphide-based semiconductor layers of the present invention, a stable boron phosphide-based semiconductor diode having the properties of a ρη junction structure can be configured. For example, in LEDs or LDs, when p-type and η-type boron phosphide-based semiconductor layers with stable resistivity are used to sandwich the cover layer of the light-emitting layer, a forward voltage (Vf) or a valve voltage (Vth) can be formed. LED or LD with dual junction (DH) structure. The light-emitting layer may include, for example, nitrogen containing a group V element such as gallium nitride / indium mixed crystal (G ax I η!. X N ·· 0 SXS 1) or nitrogen (N) and phosphorus (p) other than nitrogen. A gallium carbide mixed crystal (GaPyNn: 0 < Y < 1) and the like. In particular, the composition of the boron-based semiconductor layer constituting the cover layer and the lattice plane with a small mismatch interval G a χ I η,. Χ mixed crystal (0 S XS 1) or GaPyIVy mixed crystal (0 < Υ < 1) When the light emitting layer is formed, a light emitting element having excellent brightness characteristics can be formed. In boron phosphide-based compound semiconductors, boron that occupies phosphorus pores at a concentration greater than the concentration of phosphorus atoms that occupies the pores can form a back-sealing sleeve with P-type conduction. Due to the addition of ρ-type impurities, stability can be obtained The p-type boron phosphide-based compound semiconductor has a function of controlling the addition amount of the p-type impurity to obtain a p-type boron phosphide-based compound semiconductor layer having resistivity and a controlled carrier concentration. In a boron phosphide-based compound semiconductor, is it larger than the occupied phosphorous space? The concentration of boron vacancies existing in the concentration of L in the atomic concentration of L can form a back-sealing sleeve with η-type conduction. Due to the addition of η-type impurities, a stable η-type boron phosphide-based compound semiconductor can be obtained. By controlling the amount of n-type impurities & $, the amount of n-type phosphatization with resistivity and carrier concentration controlled can be made -15-578209 5. Description of the invention (彳 4) The role of the compound semiconductor layer. [Embodiment] The present invention is specifically explained by using p-type and η-type boron phosphide (BP) semiconductor layers provided on a silicon single crystal (silicon) substrate and constituting a boron phosphide-based semiconductor light emitting element (LED) as an example. . A schematic sectional view of the LED 1 B in this embodiment is shown in FIG. 1. For the single crystal substrate 101, a P-type silicon single crystal having a (1 1 1) crystal plane as a surface and boron (B) added was used. On the surface of the substrate 101, a zinc-doped (111) was formed at 1 050 ° C by a normal pressure MOCVD method using triethylboron ((C2H5) B3) / phosphine (PH3) / hydrogen (H2) system. -a lower cover layer 102 made of p-type boron phosphide (BP). In addition, the supply of the V / III ratio (= PH3 / (C2H5) 3B) was set to approximately 1 1 5 during the formation. From the analysis using laser Raman spectroscopy, it can be seen that the concentration of boron that occupies phosphorus pores in an undoped BP layer grown at the same temperature and the same V / III ratio is greater than the concentration of phosphorus that occupies boron pores. Its amount is about greater than ixi019cm · 3. The doping source of zinc is a dimethylzinc ((CH3) 2Zn) -hydrogen mixed gas (volume mixing example = 1 00v ο 1 · ppm), and the carrier concentration of the lower cover layer 1 0 2 is about 1 X l〇19cm · 3. The supply of dimethyl zinc is 2 × 10-6 moles per minute (mol). In addition, the lower cover layer having a layer thickness of about 400 nm is composed of boron phosphide (BP) with a forbidden band width of about 3 eV at room temperature. A light emitting layer 103 made of hexagonal wurtzite crystal type ^ -type gallium nitride • indium is formed on the lower BP cladding layer 103 of cubic sphalerite crystal type (Sphareli te). The Q6 layer of the light-emitting layer is made of trimethylgallium ((CH3) 3Ga) / dimethylindium ((CH3) 3In) / amine (NH3) / gas (Ar) / hydrogen (H2) -16- 578209) Description of the invention (15) is a normal pressure MOCVD vapor phase growth method, which is grown at 850 ° C. The carrier concentration of the light-emitting layer 103 is about 2 × 1018 cm · 3, and the layer thickness is about 600 nm. The photoresistance (PL) spectrum formed by the light-emitting layer 103 when an ammonia (He) -cadmium (Cd) laser light having a wavelength of 3 to 25 nm is incident is shown in FIG. 2. The center wavelength of PL light is about 427.5 nm. In addition, the incident intensity of the laser light is about 7.20 mV when the incident intensity of the laser light is about 0.2 mW, and the half-width of the blue-violet PL spectrum is about 3 7 8.6 meV. On the light-emitting layer 103, a boron phosphide (BP) layer is used. The above-mentioned atmospheric pressure MOCVD method used in the film formation was performed at 850 ° C to form an upper cover layer 104 made of a tin (Zn) -doped n-type BP layer. In addition, the V / I I I ratio (= PH3 / (C2H5) 3B supply ratio) was set to approximately 100 at the time of formation. When analyzed by laser Raman spectroscopy, the concentration of phosphorous that occupies boron vacancies in an undoped BP layer grown at the same temperature and at the same V / III ratio is greater than the concentration of boron that occupies phosphor pores. Approximately 3 X 1019cm · 3. The doping source of tin was tetraethyltin. The supply of tetraethyltin was 1.0 × 10 · 6 mol per minute, and the carrier concentration of the upper cover layer 104 was adjusted to 4 × 10 19 cm_3. The forbidden bandwidth of the n-type BP layer of the upper cladding layer 104 at room temperature is obtained from the correlation of the absorption coefficient wavelength (photon energy) and is about 3 eV. The thickness of the upper cladding layer 104 is about 400 nm. A circular shape made of a gold-germanium (Au · Ge) alloy is arranged in the center of the upper cover layer 104 of the multilayer structure 1A formed of the single crystal substrate 101, the lower cover layer 102, the light-emitting layer 103, and the upper cover layer 104. (Diameter = ΐι〇μιτ1) 2 ohmic n-type surface electrode 105. In addition, an approximately ohmic p-type inner electrode 106 made of aluminum (A 1) is provided on the inside of the p-type silicon single crystal base-17- 578209 V. Description of the invention (16) plate 1 0 1 to form a pn junction type LED1B with double hybrid structure. After the electrode materials are melted on the two electrodes 105 and 106, an alloying heat treatment is performed at 42 (TC under a nitrogen gas flow). 20 mA is applied to the n-side up LED1B. A current flowing in the direction (f oreward) can obtain the characteristics described in the following items (a) to (d): (a) Luminous center wavelength: about 430nm (b) Brightness: 0.8cd (c) Forward voltage: 3V ( d) Reverse voltage: 8V (reverse current = 10μA) Especially, the lower and upper cover layers 102 and 105 sandwiching the light-emitting layer are composed of a high-carrier-concentration η-type or ρ-type boron phosphide layer. A blue-violet LED with low voltage is emitted in the direction. In particular, the cover layers 102 and 105 are made of a single boron phosphide and have a sufficiently wide forbidden band width to transmit light. Therefore, a high-purity blue-violet LED can be provided. [Effects of the Invention] The present invention is formed on a single crystal substrate provided with silicon and the like, and contains boron vacant pores and boron occupies pores, and contains boron and phosphorus containing boron and phosphorus as constituent elements. In a boron phosphide-based semiconductor device based on a semiconductor layer, a When a boron-based semiconductor layer is grown in a vapor phase, it has boron containing porosity containing pores having a phosphorus atom concentration higher than that of pores occupying boron in an undoped state, and has a group II element or a group IV added thereto. Ρ-type impurities of elements can be used to produce ρ-type boron phosphide-based compound semiconductors -18-578209 V. Description of the invention (17) The layer of boron phosphide-based semiconductors with stable resistivity or carrier concentration can provide, for example, electrical properties A boron phosphide-based semiconductor device with excellent characteristics. In an undoped state, it contains phosphorus containing boron pores having a boron atom concentration higher than that of pores occupying phosphorus, and has a group IV element or a group VI added. Elemental n-type impurities and n-type boron phosphide-based compound semiconductor layers are formed, so using a boron phosphide-based semiconductor layer with stable resistivity or carrier concentration can provide, for example, boron phosphide-based semiconductor devices with excellent electrical characteristics. In the present invention, in a suitable temperature range for vapor phase growth of a boron phosphide-based semiconductor layer, by adding an element that does not easily form a polymer with boron as an n-type or p-type impurity, an n-type or p-type transmission is prepared. The conductive boron phosphide-based semiconductor layer can suppress the resistivity instability of the porosity concentration variation caused by the formation of the boron polymer. For example, the boron phosphide-based semiconductor layer with a high carrier concentration can be stabilized. The conductive layer with a carrier concentration can achieve the effect of producing, for example, a power-saving boron phosphide-based semiconductor light-emitting device with a low forward voltage. The present invention is on a single crystal substrate and has a temperature of 1000 to 12 ° C. Next, as for the raw materials of the group III constituent element of Fengdi, the supply ratio of the raw materials of the group // constituent elements is within the range of 70 to 150, and the p-type impurities of the group π or group IV elements are added to form Since the p-type boron phosphide-based semiconductor layer can reduce the amount of acceptors consumed for the donor components remaining for electrical compensation, it can stabilize the high-carrier concentration to form a low-resistance p-type boron phosphide-based semiconductor layer. In addition, the present invention is based on a single crystal substrate at a temperature of 75 ° to 100 ° -19- 578209. V. Description of the invention (18) ° C. The supply ratio of the raw materials is in the range of 70 to 150, and η-type impurities of Group IV elements are added to form an η-type boron phosphide-based semiconductor layer. Therefore, it is possible to reduce the η-type consumption of the remaining acceptor components for electrical compensation. The effect of stably forming a p-type boron phosphide-based semiconductor layer with a low resistivity at a high impurity concentration and stability. [Brief description of the drawings] [Figure 1] This is a schematic diagram of an LED cross section according to an embodiment of the present invention. [Figure 2] This is the PL spectrum of the light emitting layer of the LED in the embodiment of the present invention. [Fig. 3] It is a stability chart of the carrier concentration of a boron phosphide-based semiconductor layer when zinc is doped and when it is undoped. [Representative Symbols of Main Parts] 1 A ... Laminated Structure IB ··· LED 1 0 1 ... Single Crystal Substrate 102 ... Lower Cover Layer 103 ... Light-Emitting Layer 1 04 ... Upper Cover Layer 105 ... n-type Inside Electrode 106 ... ρ Type Inside electrode -20-