高品質無転位ゲルマニウムシリコン固溶体バルク単結晶の育成と基礎物性の解明

高品質無転位ゲルマニウムシリコン固溶体バルク単

結晶の育成と基礎物性の解明

著者

米永 一郎

高品質無転位ゲルマニウムシリコン固落体

バルク単結晶の育成と基礎物性の解明

研究課題番号13450001

平成13年度∼15年度 科学研究費補助金

基盤研究(B) (2)研究成果報告書

平成16年5月

研究代表者 米永一郎

(東北大学金属材料研究所助教授)

高品質無転位ゲルマニウムシリコン固溶体

バルク単結晶の育成と基礎物性の解明

研究課題番号13450001

平成13年度∼15年度 科学研究費補助金

基盤研究(B) (2)研究成果報告書

平成16年5月

研究代表者 米永一郎

(東北大学金属材料研究所助教授)

はじめに

ゲルマニウムシリコン(Gel_xSixまたはSixGcl_Xとも称す)は組成XによってGeか

らSiまでの間でバンドギャップを0.72から1.leVまで､格子定数を0.566から0.543mm

まで任意に変えることができる全率固溶体である｡そのため､バンドギャップ及び格

子定数制御工学用材料として注目されている｡各種のエビタキシャル法によって育成

される薄膜GeSiは超高速･可変波長発光の新しいデバイスとして､現在のSiに変わ

る材料として開発され､ IBMや東芝･NECなどで実用化が進められているが､基板と

の格子不整によって界面に転位が誘起され素子特性が劣化するため､その制御が課題

である｡また､バルク結晶&siは熱電エネルギー変換と太陽電池材料でもあるが､

現状では変換効率が低く､衛星用電源などに用途が限定されている｡それらに共通す

る問題点は､良質のバルク単結晶が組成的過冷却の発生のために得られず､転位の発

生と制御に関する知識及び変換効率を支配する熱と電荷の移動に関する基礎過程が明

らかにできないことである｡それらの基礎的物性は薄膜ではなく､バルク単結晶を用

いて初めて解明が可能である｡一般的に基礎研究を展開する観点では､薄膜ではなく､

ある程度の大きさを持ったバルク状の高品質結晶が不可欠である｡良質の単結晶を育

成することができれば､それは薄膜GeSiを含めた各種材料のエピタキシャル成長の

ための､ミスフィットによる転位の発生がない格子整合基板材料として非常に有用な

ものとなる｡また､ Ⅹ線回折結晶学においてもSiとGeの間を埋めるモノクロメータ

として熱望されている｡さらに､基礎研究によって､このSiとGeが完全に浪合した

特異な結晶に潜在する性能を明らかにすることができ､ GeSiの高性能化と応用を広げ

ることができる｡そのように期待されるGeSi結晶であるが､問題は組成的過冷却が

発生しやすく､良質のバルク単結晶が得られないことである｡

そのような観点で､我々はこれまで&Siのバルク単結晶の育成を試み､そして､

単結晶を用いた基礎物性の解明を進めて､平成13年度∼15年度に科研費基盤研究B

として補助金を頂いた｡ここにその成果を報告する｡

研究日的

本研究は(I)全組成域の高品質･低転位密度さらに無転位のGeSi単結晶を育成す

ること､そのための技術と基礎知識の確立､ (2)育成した&Si単結晶により電荷移動

度などの電子物性と結合距離､長周期規則性等の原子構造の基礎的解明､ (3)結晶中

の転位の発生と運動特性の評価とその抑制の知識の確立､ (4)育成単結晶の熱電変換

特性の解明と機能性素子としてのフエージィビリティスタディー､ (5)それら基礎知

識の確立と産業界-の提供を目的とする｡

主たる成果

1･チョクラルスキー法により0から0.15までと0.735から1までの組成Xで､直径30mm､

長さ100-のGel_xSix結晶を育成した｡特に､これまで一つの限界とされていたSi

組成が0.80以下の結晶について､世界ではじめて育成に成功した｡さらに､ネッキ

ングと育成した結晶から切り出した種結晶を用いて､転位密度が102cm-2の低転位

密度の結晶を得た｡また&Si結晶の電気的特性を制御するためB､ p､ As等の電荷

不純物､さらにSn､ C､ Fe､ Bi､ Ni等の不純物を最大濃度1020cm･3まで添加した結

晶を育成した｡また､それらの育成においては自動育成化を進めた｡

2･育成した結晶の欠陥構造をⅩ線回折顕微鏡法によって調べ､ &Si結晶では転位が

結晶の外周部のみに限定的に存在すること､また転位密度が104cm-2以下であること､

それがこの結晶系において転位の運動が抑制されるためであることを明らかにした｡

3･結晶の原子局所構造をNAS法と蛍光X線ホログラフィ法により調べ､ 4配位完全

ランダム配置であること､良一Ge､ Si-&､ Si-Siの各原子間結合距離は異なり組成に

対して線形に変化する不完全pauling型構造であることを得た｡さらに第-原理計算

からもそれらの原子間の結合距離の組成に対する依存性を良好に再現した｡

4･育成結晶を赤外吸収分光法によって調べ､結晶中には最大濃度1018cm-3の不純物

酸素が固溶し､その酸素はSi-Si結合の原子間位置を優先的に占有すること､それが

Siと0の結合力がGeと0の結合力に比べて造かに強いためであること､さらに､

その準Si-0-Si分子は上記のSi-Si結合距離の組成依存性によってその振動数を変える

ことを見出した｡また､酸素を含まない結晶の育成法を開発した｡

5･育成した単結晶を用い&Si固溶体の力学的特性を調べた｡固溶体中で運動する転

位の運動速度を応力と温度および組成の関数として世界に先駆けて明らかにした｡次

に､図2に示すようにGeSi固溶体の強度がGeやSiを凌駕し､かつ温度の上昇に伴

う強度の低下がないことを兄い出し､それが固溶体における転位の微視的な運動過程

に起因する機構を明らかにした｡

6･各種不純物を添加した結晶の熱伝導率､熱電能､電気伝導度､ホール移動度､電荷

密度等を800℃まで測定し､組成と温度､不純物の種類と濃度の関数として定量化し

た｡それに基づいて､熱電変換材料として高い可能性が得られたため､高温用ベルチ

ェ熱電変換素子-の実用化を進めている｡

今後の展脚

本研究では困難とされる固溶体の高品質単結晶の育成に取り組み､その単結晶を用

いてその基礎物性とその発現機構を電子構造と結晶構造の両面から同時に調べて明ら

かにし､そして応用のための知識を確立することを行った｡その大きな成果の一つと

して､ Si組成が0.8以下の結晶が得られたが､それはGeSi結晶を基板としてSi薄膜を

成長させることで薄膜Siに対する物性制御が可能になり､電子の移動度を高速化した

電子デバイスの性能の向上の可能性を飛躍的に推進するものである｡さらに､界面で

ミスフィット転位の発生を伴わない､薄膜･基板系の選択肢が拡大し､欠陥による劣

化の起きない高性能の発光､フォトニクス､導波管など各種機能性デバイス用の高性

能化･実用化､格子定数制御工学材料として現在Geやsiなどに限られる放射線用の

モノクロメータ結晶の利用波長範囲を拡大でき､高感度のⅩ線･中性子線などの放射

線検出器として利用できるようになった｡また､基礎研究の観点で､単純な結晶構造

で高品質･高純度な固溶体として､この結晶を用いることで､各種の原子構造､電子

構造や散乱機構などの基礎研究が進み､この材料の潜在するポテンシャルの探索と開

発､高性能化に応用することが可能になったと考える｡実際､それらの成果の一部は

国際学術論文や国際会議で発表したが､特に海外の基礎物理学分野の研究者に注目さ

れ､陽電子消滅､固溶体中の拡散､格子振動や発光､中性子分光等の基礎学術分野の

研究の試料として提供を求められており､世界的な拡がりを見せている｡それらの共

同研究の成果は今後発表されるであろう｡

中間組成の結晶については､以前シード直下での数ミリ程度の単結晶に留まってい

るが､これを克服し､全組成域について結晶の基礎物性の解明を進める予定である｡

皆様のご支援を期待するものである｡

研究組曲

研究代表者

研究分担者

研究分担者

研究分担者

研究分担者

研究分担者

研究分担者

米永一郎

阿部 孝夫

後藤 孝

進藤 大輔

Mchedlidze, T. R.

棲井雅樹

深田直樹

研究分担者 明石孝也

(東北大学･金属材料研究所･助教授)

(信越半導体･半導体研究所･研究主幹)

(東北大学･金属材料研究所･教授)

(東北大学･素材工学研究所･教授)

(東北大学･金属材料研究所･助手)

(東北大学･金属材料研究所･助手)

(東北大学･金属材料研究所･助手)

(平成14年8月15日まで)

(東北大学･金属材料研究所･助手)

研究協力者

鮎沢輝和(研究生)､ sluiter, M. H. F. (東北大学･金属材料研究所･助教授)､

川添良幸((東北大学･金属材料研究所･教授)､中嶋正雄

研究鼓費

平成13年度

平成14年度

平成15年度

7,200,000円 4,200,000円 3,500,000円

合計

14,900,000円

丑麦飴文_｣全臣ヒ且≧_題)

2001年度

1･ Dklocation bdlaviorinheavily impuritydqped Si: Viewpoint set on Ihlocation mobility

in snicon

Scripta Mater. 45 (ll), 1267･1272 (2001).

2･ Thernaland elecbicalpropcrtleS OfCzochralski grownGeSi single crystals

I. Yonenaga, T. Akashiand T. Goto

J. Phys. Chem. Solids 62 (7), 1313･1317 (2001).

3･ Czochralski grow血ofheavily impurib, doped crystals of GeSialloys

I. Yonenaga

J. Cryst. Growth226 (I), 47･51 (2001).

4. Bond lengths in Gel-xSix crystallinealloys grown bythe Czochralski method

I. Yonenaga and M. Sakurai

Phys. Rev. B 64 (ll), 113206 (113) (2001).

5. hterstitialoxygen in GeSialloys

I. Yonenaga, M. Nonakaand N. Fukata

Physica B 308-310, 539-541 (2001).

6.Lew tenperatuJTe nuOniumbehaviour in Cz･Siand Cz-SiO.9 1GeO.09

P. J. C.Kingand I. Yonenaga

Physi'ca B 308-3 10, 546･549 (2001).

7. Hightemperature tran甲Ort Properties of B-and P-doped GeSi single crystals prepared

by a CZDChralski method

T. Akashi, Ⅰ. Yonenaga, I. Chji血imaand T. Goto

Materials Transactions 42 (6), 1024-1027 (2001).

8. GeSi single crystals asthermoelecbic materials

I. Yonenaga, T. Akashi, T. Gotoand S. Yamaguchi

Proceedings onthe 19thInternationalConference on "Themoelecbic,''htemational

Themoelecbic Society, 2000.8.20-24, Cardiff(UK), 170-173 (2001).

9. Gel_xSix bulk crystals

I. Yonenaga

"The Encyclopedia of Materials: Sicenceand Teclmology", edited by K. H. J.

Buschow, R W. Calm, M. C. Flemmgs, B. IIsclmer, E. J. Kramerand S.

Mahqian,   EIsevier Science,   200 1 ,

httt):〟W.elsevier.com/mrwclus/15/178/52nndex.ht申 (辞典)

2002年度

10.lmpurib, effects on dislocation acdvitiesinSi

I. Yonenaga

J. Phys.: Condens. Mater., 14 (48), 13179113183 (2002).

ll. LocaLs加cture around Si atoms in GeSialloy semiconductors

I. Yonenagaand M. Sakurai

Photon Factory ActivityReport 2001 (No. 19), p. 176 (2002).

12. Gmwthand血ndamentalproperties ofGeSi bulk crystals

I. Yonenaga

Proceedings of the 12thInternationalconBerence on Scmiconducting & hsulating

MaterialS, 2002, IEEE PJ), p. 87192.

13･ X-ray topographic obscrvadon of dislocation generation atthe seed/crystalinterface of

Czochralski-grownSi highly doped withB impurity

I･ Yonenaga, T･ Taishi, X･ Huangand K･ Hoshikawa

Mater･ Sci･ Eng. B 91-92, 192-195 (2002).

14･ Dislocation behavior in heavily germanium-doped Si crystal

T･ Taishi, X･ MI Huang, I･ Yonenaga and K. Hoshikawa

Mater･ Sci･ in Semicond･ Processing 5 (4-5), 409-4 12 (2002).

15･ Thermaland elecbicalproperties ofCzochralski grown&Si single crystals

I. Yonenaga, T. Akashiand T. Goto

Materials Research Socieb, Symposium Proceedings of Thermoelecbic Materials 2001__

Research and Applications, edited by G･S･ Nolas, D･C･ Jolmson, D･G･ MandruS, Vol. 691,

G7.4 (2002).

2003*&

16･ Dynamic characteristics of dislocations in Ge･dopedand (Ge+B) codoped silicon

I･ Yonenaga, T. Taishi, X. Huangand K. Hoshikawa

J･ Appl･ Phys. 93 (I), 265-269 (2003).

17･Lecal s加cturearotmd Si atoms in GeSialloy semiconductors

I. Yonenaga and M. Sakurai

Photon Factory ActivityReport 2002 Po. 20), p. 160 (2003).

18･ Muonium behaviour in Czochralski grownSil-xGexalloys

P･ J･ C･King, a L･ Lichtiand I･ Yonenaga

Physica B 326, 171･174 (2003).

19･ Hydrogen behaviour in bulk Sil xGexalloys as modeled by muonium

P･J･C･King, RL Lichti and II Yonenaga

Physica B 3401342, 835-839 (2003).

20･ LocalstrainrelaxatiOn in Czochralski-grownGeSi bulkalloys

I･ Yonenaga, M･ Sakurai, M. Nonaka, T. Ayuzawa, M.H.F. Sluiter and Y. Kawazoe

Physica B 340-342, 854-857 (2003).

21. Dislocation-ImpurityInteracdons in Silicon

I. Yonenaga

Getteringand Defect Engineerlng in Semicondctor Teclmology 2003, Solid State

Phenomena Vol･ 95/96, edited by MI Kitder and H･ Richter, Trams Tech Publications Ltd,

2004, p. 423-432.

22･ Localatomic shcture in Czochralski-grownGel-xSix bulkalloys

I. Yonenaga, M. Sakurai, M.H.F. Sluiterand Y. Kawazoe

国政会議_ 国内金島での集表(合計: 21件)

2001年度

2001.5.8.  RAISSian Academy of Sciences, hStitute of Solid State Physics

(ChemogolovkarMos cow, RAISSia)

* CZTgrOWthof GeSi anoys

200 1. 5. 1 1.  Albert･Ludwigs･Uhiverstiat Freiburg, KristallograPhisches hditut伊reiburg,

Gmany)

* CZ-growthof GeSialloys, HightemperatLm hardJWSS Ofwide-band-gap

semiConductors

2001.7.15･20. 21th htemational Conference on Defects in SemiConductors (Giessen,

Germa町)

* hderstitialoxygen in GeSialloys, I. Yonenaga, M. Nonaka and N. Fukata

** Low tenperattm muoniumb血aviour in Cz･Si and CzISi0.9 1GeO.09, P. J.

C.King and I. Yonenaga

2001.ll.26･30 MamialResearch Society2001 Fall Meeting βoston, USA)

* Thermaland Elec廿icalProperties of Cz∝hralski GmwnGeSi Single

2002.03.25.

2002年度

2002.6. 17-21. 2002.6.30-7.5 2002. 9.7. 2002. ll.3.

2003.1. 15-17.

2003.3. 19-20.

Crystals, I. Yonenaga, T. Akshi and T. Goto

日本物理学会02春(57回年次大会)

辛 GeSi混晶中の格子間酸素(米永一郎､深田直樹､野中将隆､鮎沢

輝万､樫井雅樹)

The European Materials Research Society Spring Meeting (Strasbourg,

France)

I Dislocation BehaviorinHeavily Germanium･Doped Silicon Crystal,エ 地X. Huang, I. Yonenagaand K. Hoshikawa

The 12thhtemationalSemiconductingand lnsul血ng Materials Conference (Smolenice, Slovakia)

* Grow血and Rmdamentalproperhes of GeSi bulk crystals, Ⅰ･ Yonenaga

(招待講演)

日本物理学会02秋

* 高濃度不純物添加Si結晶の転位の運動特性

日本金属学会02秋 シンポジウム

* シリコン単結晶中の希薄ゲルマニウムの局在構造 (林好一､

高橋幸生､米永一郎､松原英一郎)

First lnternationalSiGe Teclmology and Device Meeting (Nagoya , Japan)

辛 Localatomic shcture in Czochralski-grownGel-XSix bulkalloys, Ⅰ.

Yonenaga+, M. Sakurai, M. H. F. Sluiter, Y. Kawazoe

電気学会 2003 奉

書ネルンスト･ゼ-ペック素子の提案､山本新､浜辺誠､高橋秀昭､

2003.3.27-30. 2003.3.28-3 I.

2003年度

2003.7.28-8. 1

渡辺和雄(東北大)

応用物理学会2003春(50回連合講演会)

* ネルンスト/ゼ-ペック素子の提案･ネルンスト/ゼ-ペック複合効

果による熱電素子の可能性､浜辺誠､高橋秀昭､山本新､山口作太

郎(中部大工)､奥村晴彦(松阪大政策)､小峰啓史(イオン工研)､

米永一郎､佐々木尚子､渡辺和雄(東北大金研)

日本物理学会03春(58回年次大会)シンポジウム:過冷却液体から

の核生成･結晶成長

I GeSi全率固溶体の結晶育成における過冷却と結晶性(招待講演)

22ndlmtemationalConference on Defects in Semiconductors (Aarhus,

Denmark)

* Hydrogen behaviour in bulk Si l･XGex alloys as modeled by muonium,巴エ

C･ King, R. L Lichtiand I. Yonenaga

** LocalstrainrelaxationinCzochralski-grownGeSi bulkalloys, i

Yonena牢a, M･ Sakumi, M. Nonaka, T. Ayuzawa, M. H. F. Sluiter, Y.

Kawazoe

2003･S･ 17-21･ 22nd International Conference on Thermoelecbics (La αande Motte,

France)

* MagnetiCfield effect for improvement ofthermoelecbic conversion: a

proposalfor Nernst-Seebeck element, M. Hamabe, S. Yamamoto, H.

Tbkahashi, S･ Yamaguchi, H･Okumura, I･ Yonenaga, T･ Sasaki,and K.

Watanabe

2003･9･21･26･ The lOthIntemational Autt- Meeting on Gettering and Defect

Engineering in Semiconductor Teclmology (Zeuthenmerlin, Germany)

* Dislocation-impurityinteraction in silicon, Ⅰ. Yonenaga (招待講演)

2003.10112-13. The 8th rUMRS Intemational Conference on Advanced Materials

(Yokohama, Japan)

* Magnetic Field Effect for Thermoelecbic Conversion : A Proposal for

Nernst-Seebeck Element, Shin YamamDtO, Makoto Hamabe, Hideaki

Takahashi, Satarou Yamaguchi (Chubu Umiversity, Japan), Haruhiko

Okumura (Matsusaka Uhiversib,, Japan), Ichiro Yonenaga, Takako Sasaki,

and Kazuo Watanabe (Tohoku Uhiversity, Japan)

2003. ll. 13-14.東北大金研研究会:熱電半導体の高性能化､

* SiGe(GeSi)結晶の熱電特性の現状と高性能化-の課題 米永一郎,

明石隆也､後藤孝､鮎沢輝万

2004･ 1･ 15-17･ Japan-Ausb･alia Workshop on Advanced Materials (Sendai, Japan)

* Atomic structureand s仕ainrelaxatiOn in Czochralski-grownSixGe 1-x

bulkalloys, I. Yonenaga, M. Sakurai, T. Aytuawa, M. H. F. Sluiterand Y.

夢肝発表

(1) ｢ゲルマニウムシリコン シリコン組成o･73 東北大､単結晶育成に成功｣

2003年3月28日 日刊工業新聞

(2) ｢ゲルマニウムシリコン半導体単結晶の大型化成功｣

2003年5月5日 河北新報

研究成果による工集所有権の出鹿･政各状況

(1)特許 GeSi単結晶製造用のるつぼ 2003-076212

(平成15年3月19日出願)

Growth and Fundamental Properties of GeSi Bulk Crystals

I･ Yonenaga

hsdbtefor M血als Research, TohoknUhiverdty, Sendai98018577, Japan

(a,mail : yonenaga@mr. tohoku.ac.jp)

I. Introduction

Gmanium-silicon (Gel-xSix or Ge-anium一点hcon SixGel_X) alloy is a Rdlymisdble solid

soludon of the diamond-baseand has atbTaCbd keminteFeSt aS material for bothmiqoelecblOnic and

optcHdecbTOmic devices inview of the poten6alfor band gapand httice param触r engineeringth町Oqer.

GeSialloysfor such apphcadonsare usually gpo- as仙n別ms on Si sub-es by various q?ltaXial

tedmiques. lJowever, in oder to clarifythefimdamentalinbmic physicalproperties of伽s material

野Stem for such血ICtionalapplicadons, it is necessary to grow highqualitybulk single crystals of GeSi alloy oflarge size Suitablefor a varietyof phy由Calmeasurements･ Bulk GeSial1oyalso has expedd

apphcadon as a photoJetector, athermc>generator,anX-rayand neutron monchromator, a solarcell

and a lattice-matched subsbdefor GeSi qpitaxid grow instead of Si. The present audlOr has

attemptedthe Czxxhrddd卵W血ofGeSi bulk crystals oflarge由ze inthe whole composition range 0 < X < 1 and succeded in growing Rdl由nde crystals of GeSialloys oflarge由ewi血nthe composidon

ranges ofO < X < 0115and O173 < X < 1 [1-7]･ Heavily impurity-doped GeSi crystals havealso been

gpo-forthe applicadon of the-decdc devices･ The su∝恕S Of growngalloy materials has

opened upthe basic research onthefundamentalproperdesthat are brmght about byalloying andthe

posdbilityof exploringthe iminsic properties ofdis teclmologiCally important material.

This resewch has beenunderbkenwiththe above･mentioned purposesunderthe support in part

bythe hts in Aid for Sciemific Research P) No･ 13450001 (aom 2001 to 2003 Academic year)

飢mthe Japan S∝ietyforthe Promodon of Sdence･ H-,血s paper rq?ortsthe some parts of the

redts on bulk crystd grow血ofGeSialloysand onthe clari丘edfimdamentalpropertiesthat have been

pdo-ed bythe author's group.

2. Bulk crystalgmwth

2.L GrlDWn COTShzb

Bulk crystals of Gel･xSixalloys inthe whole composition range o < X < 1 Wen grovm bythe

C2XX:hrdski technique at very low pulling rates ranging &om 1 to 8 mm瓜in diameterand longer than 40 zTm). Seeds prepared鮎m a Si or Ge crystaloriented parallel to 【111] or l001] orientadon were

Fig･ 1･ Si-rich Gel-xSix anoys gmwn by也e Fig･ 2l Ge.rich Gel-xSixalloys gmwn bythe C2XXhdski techmiq雌widl a Si seed crystaloI CZXX;hralski techmique･ The composidons at也e

【00l] orientadorL The compositions at dle gFOW血starting p血ons are杓= 0･03, 0･10,

gmwdl Starting rKXSitions aze杓- 0.85, 0.73, 弧d 0.15血m die le氏 boule to鮎right one, and 0.85血m也e le氏boule to也eright one, resrdvely.

FeSpeCdvely.

Figure 1 shows some of Si-rich bSialloy crystals groⅥm The cen血I boule was grown

ibm the melt ofimitial00m押SitionxhD - 0･39血血a pdlhg rate 1 mm胤 The compWidon at gFOd

imi血血n was xb - 0.73. Bodl Side crystals were grown bm a meltち瓜- 0.69 at a pulling rate of2 mm瓜 The starting composidon was x0 - 0.85 aJd也e ending compsidon of血Ieftandright side boules were O･75 and O･82,憎p∝血ely･ Figure 2 shows some of Ge>rich GeSi auoys･ The compslbons at groqA imitiadon of die bules血m the lea side were初- 0･03, 0･10 and O･15,

res押C血ely.. The leftand cemd crystals were grOwnat a Puuhg rate of2 mm瓜andtheright crystal was grown at a pdbg rate of 1 mm瓜 The development offoW (111i facets on血boules00血S

血gFOW血ofa shgle crystal matedal. Fdl single crystals oflarge size (i･e･ larger山肌25 rrmin diameter and longerthan40 rrm in lengh) were stN3ccSSRdly grownfor也e anoys of00mpSidorLS 0 < X < 0.15 and 0.73 < X < 1, de sm姐Single crystalparts mar die Seeds of也e hgots pFOvidedalloys of

irdermediate composidonforthe trarLSition to polyiCryStallimibT, Odginahginthe MurrenCe Of

constitLdonalstqx:r-00olhg l2]. The soICalld Dash neckngwidl a他山arbd long neck part was attempted in伽grow血of也e Si-rich GeSi crystalSwi血low density of grown-in disl∝血on densityas

sbwninFig･ 3･ Inthe丘gure,the boule grownwitha GeSi seedwidlthe same composlhonobtAmed

I em

I -I-抽

堅二二二二二二⊥ Fig. 4. Gel-xSixalloy crystals heavdy doped

with(a) Ga,仲) B and (C) P g拍wn by也e

Fig･ 3･ GeSi txJules (lea) grownwidl Dash Czochralski methd Compsitions at也e

nechng and (h如) grownwidl a GeSi seed

gmw血imitiadonpointare(a)初-0.95,仲)xo-widl也e same00m叩Ibon.        0.95 and (C) xo = 0.90.

血ily dqpedwidl impurityOx)mn, galliumaJkL phoゆorus)witha concemtradon up to 1020 cm-3 were

also stKX3eSSRdly grown bythe CZXX:hralski medlOd as seeninFig. 4 [7].

2.2 chat gTIOW功vdo砂

The cri血algrow血velocityvcfor也e imitiadon of polyCrystaJhzadon caused by也e consdttAionalsuper-C00hg磁l tX: estimated as a hcdon of the compslhon x bythe following

叩血on:

vc=D∇伊k/ VT;X(k- I), (k>1)       (1)

usingthe dis山budon c∝lEcimt k arbd di血sion c状tEcierlt D - (30 124 X)･ 1015 cm2/S 【8]. VO is伽

temperaAJre gdientin伽melt and ∇n is血∋ slopeof也e liquidus. Figure 5 shows也e cridcalgrow血

vel00山es estimatdfor也e temrxnture gradient of 50 K/cm as a血ndon of the composidon. The experimentalresults inclding也ose rqEX)reed previously lll7] are superimpsedinthe丘gure. The hnsidon丘om a single crystalto a ply{rystallimibr seems to o∝ur atthe pulhng rate lower thanthe

鮮血血cdtiCal即)W血velocj也eqxxiauyin也e Ge･hchalloys. Posslbly,the temperature gadient

is reduced since lower tmrxntupes aze necessazyfor也e grow血ofthese GeSi anoys. In addidon, large boule diamete指and highFOtadonalrates may disturb也e set up of homogeneous di血sion hyers at

50        1 00

Si at%

Fig. 5. Gmw血-vel∝旭es of GeSi

crystals as afimcdon of composlhon.

Solid line showsthe esdmated cridcal

grow rates for a temperahwe gadient

of50 K/m. Open circles correspond

tothe grow of singe crystals, whne

solid dJdes correspond to omce of

polyやStallizadon at a l如e sbge of the grow血and nearthe seed.

the crystal/meltinterfaaand血s may resultinconstihJtionalsupercwlingand polycrystalli22ldon.

2.3 SpaM lW肋n of肋e co〝pOSh払n ofGhSi a恥

Spadalvariadon of the alloy compoS紬on in a groⅥm CryStalwas quanbtadvelyanalysed by

m助ms OfEDX specb10SCOPy. AcrosstheinterfTace betwemthe Si seed crystalandthe growalloy

crystal,the abrupt variadon of the compo5紬皿was observedinGeSial1oys grow丘omthe melts of the ini血l compodtions higherthan屯10 - 0.050 unlike a long bnsient inthe compo由tion rq)Orted for a

G盛i crystalgrow bythe BridgmanmedlOd. Thethickness of such a transient喝On Was Supposed

to be lessthan 50 pm. Co山wily,the gradualincrease of composition was obsewed in GeSi crysds

grow by uslng a Ge seed. Exceptthe seeding and grow血initiadon prcKXtSS,forany gr… Crystal the composはon changes spadal1y in such a waythatthe Si content gadually decrewalongthe pulling

direcbon, lmPlyingthat Si inthe melt is preferendal1y constmedand takenintothe crystalduringthe

grow血【2]. The compo血onalvariadon dmingthe grow血PrcKXS Was Calculated according tothe

Sdleils'S reladon of the complete m氾ng Ofthe melt

X - xh.払(1-g)ち-1, ₍₂₎

where isthe inidalcomposition of the melt. The equilibriumdisbibudon coeBicient ko is obtained 丘omthe phase diagram, depending onthe melt composlbon.  Figure 6 showsthe evaluated compo由donalvariadon agalnStthe solidi丘cadon rado forthe various imitialmelt composidon togedler

withthe experimentalresults. It is seenthatthe generaltendenqy inthe composidon variadonswith

the solidi丘cadon rado is in agreementwithexpenmentalresults. How即er,there is discrepandes in

the values of the composition. Thus,the composition variadon of a grow GeSi crystalalongthe

pulling diredon canbe explained sa丘sfactorily bythe00ndition of complete mlXlng Ofthe melt usLng

the equilibriumdisbibudon ∝戚ci叫obtained丘omthe phase diagram, taking into acco皿tthe gravibf

( S l u J ) と p o ︻ ○ > L J P O J 9

eqect caused by a large differenceinthe densities ofGe and Si.

2.4. Lb'buk'on coeBhnt ofiwu肋

The evaltnted disdb血on c∝氏cients of various doparrtsinthe GeSialloys ale Shownin T払le 1,incomparisonwiththoseinpue Si 【9]. The obtained distribution c∝氏cients for B and P

w粥dmost independent of也e impuribl comcentradon,也e ahoy compsition and也e pul1hg rate. Dold etal. rqprted dnt也e disbibudon c∝Bicients ofAl, Ga, In, P,Asarbd Sb impurities were close to

也oseinplqe Geinshddy impuribr doped Ge･rich Sも.05Gq).95 grOwnbythe vertiCalBridgeman

medlOd l10】. Onthe odler hand, Kamomik et al. reprted a large magmitude of也e disbibution c伏IEcient of Ga ofO.3inSio.15Geo.85 [11]. However, dleir impuri呼Concenbdon ranges were radler low h die Present Study on heavily do匹d Si-rich GeSi (0,80 < X < 1)the estimated distribuhon

c∝瓜cients of也e impuritiesinGeSialloys aLe higher也m dlOSeinSi. It canbe stqpsedthatthe

incorporadon of Ge atoms of large abmiC size may lead to enhanced segregadon of也e impudbesin

GeSialloy crystals as comparedwidl Pure Si crystals.

Table 1. DishbtdonL C∝Bicient ofB, Ga弧d P impuritiesinGel-xSix in compansonwith

thatinpure Si Oief. 9).

Impurity

ﾕ

6ﾆ

儡i

X-0.8 rﾓ 纉 X-0.95 B ﾓ 纈 ∼1.2 ﾓ 0.8

Ga

0.008

P 繧 ∼0.6 纈ﾓ 0.35 5 0 ● 一 u a I t t 0 3 ! S

2.5 GrlDWn-im御

FiguFeS 7and 8 show X-ray topographic images ofplates cut鮎m a Sio･73Geo17 CryStaland a Ge"5Si｡95 Crystal, reSPeCdvely. The Si cmtent of the plates parallel (Fig･ 8a)and perpendicular伊ig1

8b) tothe grow axis were detemined to be x ∼ 0･95 and ∼ 0･93･Ascleady seeninFig･ 3a,

did∝血ons ofa highdensityare generated丘omthe Si seed/GeSial1oyinterBace･ The disl∝血ons in the seed were generated due tothe die-alshock of the seeding pnx恕Sl 0nthe other hand,the

did∝血onsinthealloy are rather s也ght, ruming nearlyalongthe grow血axis･ The Burgers vectors

of the disl∝血〉ns were found to be pardlel tothe interGace･ That is,the did∝血onsareunderstd

Fig･ 71 X-ray topographic images of a Gel-xSix crystal

ofxb - 0.73. The amws showthe di缶adon vectors

-220.

Growth direction

==コ

Seed Crystal

(a)

Lb)

Fig. 8. X-ray topographic images of a Gel-xSix crystalofxb - 0･95･ (a) hage of the parallel plate

and (b)that of the perpendicularplate tothe grow axis･ The arrows showthe di缶action vector

to odginateinorderto amodatethemiat sb血attheinterface･ hthe plate perpendiculartothe

grow axis Fig･ 3b,fine concendc drcles) sowed shjbblonsare apparent The variadon of

composition related to suchfluchladon was smallerthanthe detection limit ofEDXanaly盛S･ White hnes n-g acrossthe sbiadons seeninthe topograph arelmages ofdid∝血ons. Such did∝血mS are mainly generated atthe seed/huoy i峨butalso加mtheperiphery of the crystalas dbsewed in

highpurityGeSialloys l1,2,3,7]･ The dendtyofgr0--in didocadonsindlealloys wasinthe range

103 - 105 cm-2･ The generah p-s may be conbued bythe maghde ofthemiBt sbain

betweentheal1町and sedthe temperahm,the temperahue卵血entandthe md'ility of generated

did∝血ons inthealloy.

Twins are血dbserved in GeSial1oys ofinte-ediate Si content. The slacking fdt

energy of GeSialloy is 55-60mJ/m2,int-ediate betweenthose of Siand Ge as seeninFig. 9 [12].

Mn generadoninGeSialloys IS not ascribed to a lower mag血de of the stacking fdt enerw but

rather related to highsbdn originadngfromthe axialcomposition variadon.

80

0   0.2  0.4  0.6   0.8  l

Si content x

Fig･ 9･ slacking fault energy of蝕Sialloys depending onthealloy comrxmhon･

3. FhdamentalpltIPertieS

3.L Local abndc肋cbwe

Extended x-ray-absorpdon血e一血lCture阿AS)甲eCblOSCOPy On die grOWII Gel-xSix

dloys inthe whole composidon range 0 < X < 1 were performed to clarifythe effect of alloy

compodtion ontheぬInic bonding of the nearest-ndghbor inthe l∝d atomic shchne l13, 14].

XAFS甲eCba of 良 K,edgeand Si K,edge were observed using血Ssion mde atthe

(

e

u

J

r

u

J

]

^

^

6

p

u

O

と

n

虐

6

u

名

月

の

BLlOBand BL-llB staion, re甲eCdvely, of XEKぜF･ The first-dleu Ge and Si00odinaGon ntmbcrs aFtWd G母and Si abms dedved Bom也e XAFS dぬare血own as a Rmcticn of alloy conlPOd丘皿inFig. 10. Here, N-G<Ge)and N-Si(Ge) meanthe CCK)Fdinadm mlmbers arowd Ge

ぬns dedved触m Ge K,edge XAFS dぬ,仙le岬Si) and NISi(Si) mcanthose around Si abms ddved bm Si K,edge XAFS data･ The dadled lines血owthe cwdimion numbers predicted fcm

randommiXhxre of Siand Ge abms. The XAFS results血ow a random sid)sdbGcn dte mpanq of Si and Ge atoms acrossthe emire00mpo血on range. The ordering parameter l0.25NGe - (1 - X)] / x

pd. 14) es丘mated加mthe Ge ccordinadon numberNBar-dthe Ge abms in bulk Gel-xSix crystals (0.44 <X<0.82), is …d 0.06 - 0.ll, farBom l･ This meansdlatnOPrefepemialode血g of the G曲dimer seems to oWinbulk GeSi crystals aqossthe whole compoS組on range.

The Ge-Gq GかSiand Ge-Si bond lengthSinGeSialloys are plo血againstthe anoy

compo血oninFig. ll. ItwaiS血皿dthatthe的GヶSiand Si-Si bond lengths maintain didncdy

diqqemt lenghsand varylinearly as afuncdm Of Si content whch is血血ar to odler Semiconductor

glqys as G血As 【15]. Atthe composi血X - 0.5the GかSi bond lengdl is 2･40 - 2･4l A,

corresponding tothe sumofthe Si and Ge covalent radh･ The observed bondingfeahue in GeSial1qys

is dose to, bd not completely,the sodluPauling limit l16] raherthanthe Vqgard limit l17]･ The

esdmated tqpologiCalrigidityparameter 0.6 suggeststhatthe bond lengthSand bondanglesare distorted.

h comparisonwiththe ab,inih'o predidons l18】, it can be condudedthat most ofthe血n in GeSi

alloys is accommodated by changes ofbohthe bond lengdl and bmdangle. The X-rayfluo憎く治nCe

hdography shldyincludingthe second neighbor atoms血owsthe sim血characteriStiC氏血Ⅰ℃s of the

atomic shchm ofGeSialloys l19].

:芸G?､､､.NJi.Ge,,.,/ts,.::

ヽ′

/:.'くも:

′ヽ

∫/､､.Q

/NJ3etS.)｡1､､_

l.6 8l Content Ge.抽 一一一一_

ヰ耳サ

0.5       1 Sl content

Fig. 10.血and Si cwdimion numbers Fig･ 11･ GかGebondlengdl(叫,dleGか

around Ge and Si atoms derived丘om XAFS data as a血ldon of Si content. The symbol ◇ isforpwe Si crystal. The dadled hnes

showthe cooFdinadon numbers predicted丘αn

a random mi血陀Of Siand Ge atoms.

Si bond lengdl (Ge>Si)andthe Si-Si bond

length(Si->Si) in GeSialloys as a血ndon of Si content. 2 ︼ 〇 一 L L l n t I L J O L P F L I F P J l O O q r )               o I _ 〇 ･ 2 .   M o ( u J u ) u 〇 一 e l S a J L e 3 L J 一 S L -0 3 9 L J q S I Q

3･2肋E Lmd肋emudprope畑由

The elecbicalandthermalproperdes have becninvesdgad at room temperabeand

elevated temperahwes forthemoelechc applicadon of the present materials.

The elecbicalconducdvib, decreases monotonicallyfrom pure Ge to Siwithincreahgthe Si

contentinundoped GeSialloys, whch is atbibuted totheinbindc canier concemdon detemined by

theband gap encrgy･AsS鰭I in Fig･ 12,the elecbTOnand hole mobilidesare comparable each otherin

GeSialloys of dleinte-ediate composidons and dlOW aminimumarotmdthe Si content 0.5 - 0.6,

which canbe explainedinte-ら ofthealloy scadng produced bythe disopdepedflu血血onsofthe

latdce potemials atthe latdce由tes l20-22]･ Similarly,thethermalconductivitywas mainly conbTOued

bythe phonon scatming due to a distordon Qfthe crystallattice, showing aminimumatx - 0.5 - 0.7 in

Fig.13.

0      0.6

Si content

Fig. 12. ElecbTOnand hole mobiliGes of

G盛ialloys at room temperahue as a

Rncdom of Si content.

0.5

Sl'codend

Fig･ 13･ The-alconducdvity ofGeSialloys

at 600oC as afuncdon of Si content.

Corpcmdon of elecbically activelmpurides leads tothe reducdon ofthcmalconducdvity

and elecb10Il and hole mobilities･ By u由ng highqualitysinde crystals of Si-rich SiGealloys, high

efEdentthemo.Clecbic pFOPer丘es have been dbtainedincomparisonwiththose previowly repodfor GeSi polycrystds ofanintemediate composition l23]. The m飽S∬ementS Ofthethermal

conducdvity(K), elecbicalcmductivity(d and Sea,eck coetRdent (a) of the heavily impuritydoped

crystals were performed inthe temp弧山re range 300 1000 K. The Sea)eck cufRcient αwas 300

-400 LAV艦at 600oC inthe impurityJoped GeSial1oys･An回vs ln (句plot ofhi曲ly

impurity-doped GeSi alloys db町S alinear relaGon as seen in Fig･ 14･ The slopeofthe sbdght line is 1.2 Me,

indicadngthe coorporadon of the charged impurib,intothealloy scadng mechmism.

(

s

N

z

u

3

)

4

!

l

S

q

O

u

l

]

t

r

H

2 0         1 0 W 堅 盲 ･ L . P M P W J Z Z ∼ u n u ○

●伸一

◆吻e

Op-opeQQTyJ

● 趙ﾖ X*柳ﾇ鋳 ●◆ ﾈ 4踐諛 B ● ﾂ

Poo

▲ ● 103      101      10S

ELtcdcd eon血didq, (QhA叫J

Fig. 14. The absohde Sea)eck cuEident of GeSialloys versusthe elecbical conducdvib, at 600oC,

血erethe data on polycrystals Geo3Sio.7 by Dismukes etal. LJ. AWL. PbiS. 35 (1964) 2899]are

plod.

3.3物〃加甲〟rO

htersdGal1y dissolved叩genぬnsinC2XX:hralski-grow Gel_xSix were invesBgated bythe

infiqed absorpdon甲eCb10SCOPy tOgetherwiththeanaly点s bythe secondary ion mass specbTOSCOPy and

the X-ray fine shlChqe l3, 24].

Fig. 15 showsthe inbred absorpdon甲eCb･a of the grow Gel_xSixalloys of various Si

content x, obtained at RT. The remarkable, broadpeak was observed a;tthe posidon centeredaround

1 106 cm-I, whidmri由nate onthe ant-Symebic sbletChingvibradon ofintersti血ly dissolved ovgen

atoms between Si atoms, Si-0-Si. The absorpdon c"Bicient 3 - 4 cm-1 was measured in Si-dch

GeSialloys, m飴Illngthat a

large number ofinterstitial

oxygen atoms are being

indudedinthealloys. No

peak at 855 cm-I onglnahng

舟αTI Ge,0-Gevibradon Ⅷ

ddDCted even in Gedch GeSi

alloys. Moreover,there is no

peak inthe wave number

range llO6 - 855 cm-1･

Thepeak intendtydeqeases

with a decrease in the Si

content x andthenthe peak

almost disappears inthealloys

with x lower than 0.23.

The pealC i血tyvariadon

【否E

鍛8

I OOO

wirVmlh由l (CrP `1 i

専諺沖

Fig･ 15･ hhred absorpdon specb･a of the as-grovm Gel･xSix

alloys of various Si contentr, measLUed at R工

o 0 O 卯         4 0         2 b ^ d 暮 p a q ? よ ｢

電

蓄

憲

愚

者

考

corresponds well tothe change of the total拡ygen COnCenbdon dctemined by Sm応, which means thatalmostall die ∝ygen atoms intheallcys are Present aS intersti6ally dissolved abms, but not as

predpi触S･ The耽ygen COnCenbdon is detemined bythe rado of Si-Si bonds in GeSialloywith

re甲eCttOthe composidon,血ee Siand Ge abms -pythe latdce盛tes randomiy･ Thus, it is found

thatanovgen abm pFeBeremially ∝mpiesthe bond,ccmtered position of Si-Si bonds,foming Si-0-Si

centers･ No peak originahg Into Si-0-Ge quasi-molecule exists in GeSialloys. Probably

oxygen atoms have a sb10ngerinteracdonwithSi atomsthanwithGe ones･ The 1106 cm-1 peak

血鮎to low軸enq ddewithanincreaseinGe, possibly due tothe expansion of Si-Si bonds as

revealed bythe XAFS shldy describedina previous section l13, 14].

3. 4 MechLmidpropudお

Uhiquefeahqe of GeSialloys mgLnahg aomthealloying has been observed ontheir

mechanicalbehavior･lmthe hrich GeSialloys ofcompodtion range o < X < 0.08the did∝adon

vd∝吋decreases monotonicallywithincreasing Si content, reaching about one of seventhofthat in

plqe Ge atx = 0108inthe tempera山托range 450 - 700 oCandthe sbleSS range 3 - 24 MPa l25]. C00血ly, inthe compo盛tion range O･94 < X < 1the didocadon velodtyfirst increasesandthen

decreaseswithincreasing Ge content inthe temperabre range 750 - 900 oCandthe sbTeSS range 3-30

MPa as seen Fig. 16 [6, 26].

Fig. 16. Velodties of 60o dislocadonsinthe

Ge-richand Si-rich GeSialloy at 550and 800.C,

respectively, tmder a sh哉汀SbleSS 20Mpa as

dq?endent onthe Si content.

The sbleWSBain behaviorinthe yield region Ofthe GeSialloys of the composition 0 < X <

0･4 is由mi1artothat of Ge at temperabres lowerthanabout 600oC 【27】. However,the yield stress becomes temperahlre,insensitive at hightemp血lreS and incFCWwithincreasing Si content. The

sb15SSISdn curves of the GeSialloys ofdle COmPOSidon range O･94 < X < 1 is simi1artothose of pure Si

at temperahues 800-1000oCandthe yield sbleSS increaseswithdeqeasing Si content l6, 26]. Figure

Fig. 17. Yleld sbleSS Ofthe GeSi

alloy plotted against the Si

contentforthe deformadon at

900oCunder a shearsBain rate

100    ofl.a x lO4S-l

1.a x 104 S･l ai 900oC･ The yidd sbTeSS increaseswithincreasing Si contentinthe compodtion rangex

- 0 - 0.4 and decreadng Si content. Theyield sb,esses ofdlealloyswithX> 0.10are much higherthan

that of pure Si･ Overthe whole composidon range of the GeSialloysthe yield sb,ess showsthe

maximumaroumd x - 0.5and be dq?endent onthe composidm aS prOPOrtionalto x(1 - X). Sincethe

elasdc constants血ow alinear dlangefromthat of Si to Gewithrespectthe composlbon, lt Canbe

supposedthat btdt-in sb,essfields related tomicroscopicfluch血on ofalloy composlbon, togetherwith

the dymamiCintdon betwem did∝血onsand solute atoms, suppFeSSthe disl∝血on activitiesand

b血g aboutalloy hardening l6, 25].

4. ConcltlSive I℃marks

Althmgheven now GeSialloyswithintemediate compo血on remain di瓜cdt to grow in singe crystalfom,the establiSlment of血table grow methods andtheknowledge onthe iminsic

materialproperdes by using bulk crystalSare importarLt hm bothfundamentaland practiCalviewpolntS･

E甲edally,血Salloy has large potendalnot onlyformicrDand opt&elecb10nic device applicaion btit

also for elecbic power generaGonunder more envirorment-compadble condidons.

Acknowiedgenents

The audlOr eXPreSSeSthe gadbde tothe Dr･ T･ Abe of Shin-Etsu HmdoutaiCo･ Ltd･ for his

encouragementand Mrs･ A Mami, M･ Nonalq T･ AyuZaWaand Ih･ M･ Sakurai, T･ Akashi, NI Fuhta

and T R Mchedlidze and Profs. T. Goto, D. Shindoand M. a F. Sluiter forthdr assistances in growng

crystalSand evaluadng various physicalpropedes･

R血ICeS

0 0           0         0         0 4 3 2 一 ー ( t ! d M ) S S a J I S P l 盟 ^

[1] Ⅰ. Yonenaga, A Matsui, S. ToZaWa, K. Sumino, T. Fukuda, J. CrystalGrod 154 (1995) 275. [2] A Mぬui, Ⅰ. Yoncnaga, K. Sumino, J. CrystalG細1 183 (1998) 109.

[3] Ⅰ. YonenagaandM. Nonaka, J. CrystalGml細1 191 (1998) 393. [4] Ⅰ. Yonenaga, Y M血akami, J. CrystalGmw血191 (1998) 399.

[5] I. Yonenaga, J. CrystalGrod 198/199 (1999) 404.

[6] Ⅰ. Yonenaga, J. Mat. Sd.: Mat. ElecbTOn. 10 (1999) 329.

m I. Yonenaga, J. CrystalGw也226 (2001) 47.

lS] W. A Tiller, K. A Jackson, J. W.叫B. Chalmers, AぬMdd. 1 (1953) 428.

[9] D.T. mllle申d.), Hmdbook ofCrystalGFOWth, Vol. 26 North-IIolland,Amsterdam, 1994, p. 8 13. [10] P. Dold, A. Barz, S. Recha, K. Prcssel, M二FranちKW. B飢ちJ. CrystalGrod 192 (1998) 125.

lll] E.K. Kamomik, E.D. Nensberg, G.V. Nikitina, A.G. Odov, V.N. Romanenko, Inorg. Mater. 4

(1968)667.

[12] Ⅰ. Yonenaga, S. -II Lim, D. Shindo, Philos. M喝. u弧80 (2000) 193.

[13] I. Yonenaga, M. Sakurai, Phys. Rev. B64 (2001) 1 13206.

[14】 Ⅰ. Yonenaga, M. Sakurai, M. Nonalca, T. Ayuzawa, MRF. Sluiter, Y. Kawazcc, Phy由ca B 340-342

(2003) 854.

[15] J. C. Mikkdsen, Jr., J. B. Boyce, Phys. Rw. Le比49 (1982) 1412.

[16] L Pauling, The NaAule Of the ChemiCalBond, Comell UmiversityPress, Itahca, New York, 1967.

[17】 L. VCgard, Z. Phys. 5 (1921) 17.

llS] M且F. Sluiter, Y. KawazoちMater. Trams. 42 (2001) 2201.

[19] K. Ihy鮎hi, Y Tbkahashi, Ⅰ. Yonenaga, E. Matsubara, Mater. Trams. (2004), in press. [20】 T. R Mchedlidze, I. Yonenaga, Mat. Res. S∝. Pr∝. 442 (1997) 381.

[21] Ⅰ. Yonenaga, T. Aka血i, T. Goto, J. Phys. Chem. Solids 62 (2001) 1313. [22] I. Yonenaga, T. A血血, T. Goto, Mat. Res. S∝. Pr∝. 595 (2001) G7.4.1.

[23] J.P. msmukes, L EksbTOm, E.F. Steigmeiq Ⅰ. Kudman, D.S. B∝rs, J. Appl. Phys. 35 (1964) 2899.

[24】 Ⅰ. Yonenaga, N. Fukata, M. Nonaka, Phy由ca B308-3 10 (2001) 539. [25] Ⅰ. Yonenaga, K. Smino, Appl. Phys. L弧69 (1996) 1264.

[26] I. Yonenaga, Phys. Stat. Sol. (a) 171 (1999) 41.

主要飴文集

1. Gel-xSix bulk crystals

I. Ybnenaga

uThe Encyclopedia of MaterialS: Sicenceand TeclmologyH, edited by K･ a J. Buschow,

R W･ Calm, M･ C･ Flemings, B･ IIsclmer, E. J. Kramerand S. Mahajan, EIsevier Science,

2001, p. 864718651.

h廿p:/h.elsevier･com血rwclus/15/178/52rindex.hQ) (辞典)

2. Czochralski grow ofGel-xSixalloy crystals

I. Yonenaga, A. Matsui, S. Tozawa, K. Suminoand T. Fukuda

J. Cryst. Grow血154, 275-279 (1995).

3･ Czochralski grow血ofbulk crystals of Gel-xSixalloys

A. Matsui, I. Yonenagaand K. Sumino

J･ Cryst･ Grow血183, 109-116 (1998).

4･ Czochralski grow血ofbulk crystals ofGe1-XSixalloys I II: Si-richalloys

I. Yonenagaand M. Nonaka

J. Cryst･ Grow血191, 3931398 (1998).

5･ Segregation duringthe seeding process inthe Czochralski grow血of GeSialloys

I. Yonenagaand Y. Mdrakami

J. Cryst. Grow血191, 399-404 (1998).

6. Czochralski grow血ofGeSi bulkalloy crystals

I. Ybnen喝a

J. Cryst. Grow血198/199, 404408 (1999).

7･ Czochralski grow血ofheavily impuritydoped crystals ofGeSialloys

I. Yonenaga

J. Cryst. Growih 226, 47-51 (2001).

8･ Dislocation dissociationand stacking-fdt energleS in Gel-XSixalloys

I. Yonenaga, S. -H. LImand D. Shindo

Philos. Mag.Lett. 80, 193-197 (2000).

9･ Bond lengths in Gel-xSix crystallinealloys grownbythe Czochralski method

I. Yonenagaand M. S止umi

phys. Rev. a 64, 113206 (1-3) (2001).

10l Localstrain relaxation in Czochralski-grownGeSi bulkalloys

I. Yonenaga, M. Sakurai, M. Nonaka, T. Ayuzawa, M.H.F. Sluiterand Y. Kawazoe

Physica B 340-342, 854-857 (2003).

1 1･ Ihsorder broademing of the acoustic branches in SixGel-Ⅹ mixed crystals

E. Rat, B. Hehlen, J. Kulda, I. Yonenaga, H. Casalta, E. Courtens, M. Foretand a

Vacher

physica ち 276-27S, 429-430 (2000).

12. Hall effect in amisotropic SixGel-x polycrystals

T. R Mchedlidzeand I. Yonenaga

Jpn. J. Appl. Phys. 35, 652-655 (1996).

13. Hall effect measurements on SixGe1-X bulkalloys

T. R Mchedlidzeand I. Yonenaga

Mat･ ResI Soc° Symp･ Proc･ Vol･ 442, Defects in Electromic Materials H, edited by J.

Michel, T･ Kennedy, K･ Wadaand K･ Thonke, 1977, p･ 381-384.

14･ Photoluminescence spectra of deformed Si-Gealloy

K･ Tanaka, M･ Suezawaand I･ Yonenaga

J･ Appl･ Phys･ 80 , 699ト6996 (1996).

1 5･ Thermaland electriCalproperties ofCzochralski grownGeSi single crystals

I. Ybnen喝a, T. Akashi and T. Goto

J･ PhysI Chem. Solids 62, 1313-13 17 (2001).

16･ Thermaland electriCalproperties of Czochralski grownGeSi single crystals

I. Ybnen喝a, T. Akashi and T Goto

Materials Research Society Symposium Proceedings of Thermoelectric Materials

2001--Researchand Applications, edited by G･SI Nolas, D･C･ Jolmson, D.G. MandruS, Vol.

691, G7.4 (2002).

17･ Interstitialoxygen in GeSialloys

I. Ybnen喝a, M. Nonaka and N. Fukata

Physica B 308-310, 539-541 (2001).

18･ Hydrogenbehaviour in bulk Sil xGexalloys as modeled by muonium

P･J･C･King, RL･ Lichtiand I･ Yonenaga

Physica B 340-342, 835-839 (2003).

19･ Dislocation velocityin GeSialloy

I. Ⅵ)nen喝a and K. Sumino

Appl･ Phys･ Lett. 69, 1264-1266(1996).

20･ MechanicalstrengthofGeSialloy

I. Yonenagaand K. Sumino

J･ Appl･ Phys. 80, 3244-3247 (1996).

211 Dislocation velocitiesand mechanicalstrength of bulk GeSi crystals

I. Yonenaga

Phys･ Stat･ Sol･ (a) 171 (1), 41-46 (1999).

J･ Appl･ Phys. 84, 4209-4213 (1998).

22. Recombination-enhanced dislocation motion in SiGeand Ge

I･ Yonenaga, M. Werner, M. Bartsch, U. Messerschmidtand E. R. Weber

Phys･ Stat･ Sol. (a) 171, 35-40 (1999).

23･ Grow血and mechanicalproperties ofGeSi bulk crystals

I. Ybnen喝a

J･ Mat･ Sci･ -Mat･ in Electronics 10 , 3291333 (1999).

24･ Plastic deformationand dislocation dynamics in semiconductors

I. Yonenaga

Dislocations, plasticityand metal forming (Proceeding of 1 OthIntemadonal Symposium

On Plasticity and its Current Applications, Quebec City(Canada), July 711 1, 2003), Eds.

A･ Khan, R･ Kamiand J･ Zhou (NEAT Press, Maryland, 2003), p. 3101312.

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