るGaNに注目し､上述の複合窒化物Li3GaN三との共存･平衡下におけるGaN
の合成を実証した｡本論文では更にGaNについて電気化学的手法による合 成法を提案し､その化学反応における､各物質が許容できるポテンシャル範 囲及び反応メカニズムは､等温化学ポテンシャル図を用いて､反応経路及び 相平衡を考察することにより理解が得られることも示した｡最後に､本研究 のサイドジョブとしてのTa粉の効果的な窒化処理に関する研究では､現在 工業的にTa粉の脱酸剤として用いているMgの窒化物Mg,N,を窒素ソース
‑･としたTa粉の窒化実験を行った.その結果から､アルゴン雰囲気における Ta粉の窒化が明瞭に認められ､窒素雰囲気中でこの方法を用いれば､今まで 以上に窒化ムラを減少させ効果的なTa粉の窒化が行える可能性について､
基礎科学的根拠を与えることが出来たと判断した｡
参考文献
1)木村勇男､堀田憲康､温井秀樹､斎藤夏風､安川三郎､ ｢AIC13とNH,の
気相反応によるAIN微粉末の合成｣日本セラミック協会学術論文誌､
96(2) (1988) pp.206‑210.
2) N･ Hashimoto, S･ Deki, H. Tato, and Y. Kanaji, "Effect ofPolynuclear Complex Content on the Synthesis ofAIuminum Nitride from AIuminum Polynuclear Complex･", J･ Am. Ceram. Soc., 77 (1994) pp.1633‑1637.
3) I. Grzegory, J. Jun, M. Bockowski, ST. Krukowski, M. Wroblewski, B. Lucznik, and S･ Porowski, HIII‑V Nitrides ‑ Thermodynamics and Crystal Growth at High N2 Pressure･'', J. Pkys. Chem. Soltldi･, 56 (1995) pp.639‑647.
4) RI Madar, GI Jacob, J. Hallais, and R. Fruchart, "High Pressure Solution Growth ofGaN.", J. Cryst. Growth, 31 (1975) pp.1971203.
5) T･ Sasaki and T. Matsuoka, "Analysis of two‑step‑grovAh conditions for GaN on
an AIN buffer layer∴ J. AIPl. Pkvs., 77 (1995) pp.192‑200.
･6) R･ M･ Ybnko, E･ Ⅵleckis, and V A. Maroni, …Solubility orNitrogen in Liquid
Lithium and Thermal Decomposition of Solid Li,N.", J. Nwc/. Mater., 57 (1975)
pp.3 1 7‑324.
7) M･ F･ Bell, A･ Breitschwerdt, and U. Yon Alpen, "The EffTect of Hydrogen on the Ionic Conductivity in Lithium Nitride.", Mat. Res. Bw//., 16 (1981) pp.267‑272.
8) Francis J･ DiSalvo and Simon J. Clarke, "Ternary nitrides: a rapidly growing class of new materials･", C1‑. OpI'n. So/idState Mater. Sci., 1 (1996) pp.2411
249.
9) ∫. M. McHale A. Navrotski, Glen 良. Kowach, Ⅵncent E. Balbarin, and F ∫.
DiSalvo, …Energetics of Ternary Nitrides: Li‑Ca‑Zn‑N and Ca‑Ta‑N Systems･M,
Chem. Mater., 9 (1997) pp. 1538‑1546.
10) Ihsan Barin, Fried Sauert, Erast Schultze‑RJ10nhof; and Wang Shu Sheng : ThermochemL'cal Data ofPuye Substances, Part I‑II, ( 1 989).
ll) M. W Chase, Jr., C. A. Davies, J. R. Downey, Jr., D. J. Frurip, R. A. McDonald, and A. N. Syverud : JANAF Thermochemical Tab/e.S･ ThifdEdittlon, Part I‑II, I‑(1985).
12) H. Yamane, S. Kikkawa, and M. Koizumi, …Preparation and Electrochemical
Properties ofDouble‑Metal Nitrides ContalnlngLithium.", J. Power SotlrCeS, 20
(1987) pp.311‑315.
13) H. Yamane, S. Kikkawa, H. Horiuchi, and M. Koizumi, …Structure of New
Polymorph of Lithium Boron Nitride, Li̲,BN2.", J. So/t'dSlate Chem., 65 (1986)
pp.6‑12.
14) H. Yamane, S. Kikkawa, and M. Koizumi, "Preparation of Lithium Silicon Nitrides and Their Lithium Ion Conductivity.", So/lld State lollics, 25 (1 987) pp.183‑191.
1 5) H. Yamane, S. Kikkawa, and M. Koizumi, …High‑ and Low‑Temperature Phases
orLithium Boron Nitride, LijBN,: Preparation, Phase Relation, Crystal Stmcture, and Ionic Conductivity.", J. Solt'dState Chew., 71 (1987) pp.1‑ll.
16) R. Juza, K. Langer, and K. Yon Benda, "Temary Nitrides, Phosphides, and
Arsenides of Lithium.…, Angew. Chem. Illterllat. Edl'1., 7 (1968) pp.360‑370･
1 7) Marten G. Barker, Peter Hubberstey, Andrew T. Dadd, and Stephen A.
Frankham, "The Interaction ofChromiumwith Nitrogen Dissolved in Liquid
Lithium.", J. NILCl.Mater., 114 (1983) pp.143‑149.
18) Thaddeus B. Massalski, Hiroaki Okamoto, P. R. Subramaian, and Linda
Kacprzak : Binary Alloy Phase Dt'agrams Second Edt'tt'on, Volume I ‑3 , ( I 990).
19) T･ E･ Warmer, D･ JI Fray, and A. Davies, "A high‑temperature solid‑state
potentiometric sensor for nitrogen based on ceramic LaAl12018N･", JI Mater･ Sct･･,
32 (1997) pp.279‑282.
20) M･ S･ Bhamra and D･ J･ Fray, "The electrochemical properties ofLi,AlN, and
‑ I Li2SiN21", J･ Mater. Sci., 30 (1995) pp.5381‑5388.
21) C･ John Wen and Robert A. Huggins, "Electrochemical Investigation of the Lithium‑Gallium System.", J. Elebrochem. Soc., 128 (1981) pp.1636‑1641.
22) C･ D･ Thurmond and R. A. Logan, "The Equilibrium Pressure ofN2 0Ver GaN.", J･ ElectT10Chem･ Soc., 119 (1972) pp.622‑626.
23) M･ R･ Lorenz and B･ B･ Binkowski, "Preparation, Stability, and Luminescence or Gallium Nitride.", J･ Electrochem. Soc., log (1962) pp.24‑26.
24) H･ P･ Maruska and J･ J･ Tietjen, "The Preparation and PropeJly of Vapor‑deposited Single‑crystalline GaN･", AIPl. Pkys., Left., 15 (1969) pp.327‑329.
'25)R･ Dingle, D･ D･ Sell, S･ E. Stokoski, and M. IIegems, "Absorption, Renectance,
and Luminescence ofGaN Epitaxial Layers.…, Pkys. Rel,. B, 4 (1971) pp. 121 1‑
1218.
26)H･ Yamane, S･ Kikkawa, and M. Koizumi, "Lithium Aluminum Nitride, Li3AlN: as aLithium Solid Electrolyte.", SolidState loTN'C.i., 15 (1985) pp.5 1‑54.
27) H･ Kimura, M･Asano, and K. Kubo, "Vaporation of Solid Lithium Nitride.", J
NIJCl･ Mater., 91 (1980) pp.200‑204.28)D･ W･ Osborne and H･ E･ Flotow, "Lithium Nitride (Li,N) : Heat Capacity kom 5 to
350 K and Thermochemical properties to 1086 K･M, J･ Chem･ Thermody〝amics, 10