·168 北京科技大学学报 2002年第2期 8 Akasaki I,Amano H,Koide Y,et al.Effects of AIN Buffer 11段树坤，陆大成.MOVPE生长GaN的准热力学模型 Layer on Crystallographic Structure and on Electrical and 及其相图[】.半导体学报，1997,18：385 Optical Properties of GaN and Ga:Al,N (0<x0.4)Fil- 12余庆选，励翠云，彭瑞伍MOCVD GaInP材料生长过 ms or Sapphire Substrate by MOVPE[J].J Crystal Gro- 程热力学及其特性[J.半导体学报，1997,18：253 wth,1989,98:209 13 Hsu CC,Yuan JS,Cohen R,et al.Doping Studies of 9 Nakamura S,Mukai T,Senoh M.Candela-class High-brig- GaIn,P Organometallic Vapor-phase Epitaxy[J].J Appl htness InGaN/AlGaN Double-heterostructure Blue-light- Phys,1986,59:395 emitting Diodes[J].Appl Phys Lett,1994,64:1687 14 Yuan J S,Chen C H,Cohen R,et al.High Quality Ga,In- 10 Lu DC,Wang D,Wang X,et al.Metal-organic Chemical P (x=0.65,0.69)Growth by OMVPE[J].J Crystal Growth, Vapor Deposition Growth of GaN[J].Materials Science 1986,78:63 and Engineering,1995,B29:58 Pyrolysis Effect of NH;and PH,on the Composition Spaces for MOVPE Growth of III-V Semiconductors LI Changrong",LU Lin,WANG Fuming,ZHANG Weijing" 1)Materials Science and Engineering School,UST Beijing,Beijing 100083,China 2)Metallurgy School,UST Beijing,Beijing 100083,China ABSTRACT Taking the Metal-Organic Vapor Phase Epitaxy (MOVPE)of GaN and(Ga-,In,)P semicon- ductors as examples,the pyrolysis effect of NH,and PH,vapor sources on the composition spaces for growing GaN and(Ga:-,In,)P compounds has been studied.According to the situation of NH,and PH,pyrolysis in ex- perimental conditions,the thermodynamic models for different pyrolysis status are built.Furthermore,the composition spaces for growing III-V semiconductors are calculated and predicted with the aid of the Thermo- calc software.The correspondence of the theoretical analysis with the experimental data indicates that for the thermodynamic analysis of MOVPE process of GaN and(Ga-,In,)P semiconductors,the calculation and pre- diction must be conducted under the conditions of the complete equilibrium or the constraint equilibrium based on the practical pyrolysis of NH,and PH,vapor sources.The analysis of the complete thermodynamic equi- librium is only applied to some specific temperature region or certain epitaxy process after typical pretreatment of vapor sources. KEY WORDS thermodynamic analysis;V group vapor source;pyrolysis;GaN;(Ga-,In,)P;MOVPE一 1 6 8 - 北 京 科 技 大 学 学 报 2 002 年 第 z 期 8 A kas ak i l , A m a n o H , K o i d e Y, 以 a l . E fe ct s o f A NI B u fl 贻r L ay e r o n C yr ast ll o gr aP hi e S trU c ot r e an d o n E l e e tr i e a l an d O Pt i e a l Por P e rt i e s o f G aN an d G a 卜 xA咖 ( 0众感 0 . 4 ) Fi l - m s o r SaP Ph ier S u b s t r a t e by M O V P E [ J ] . J C yr s at l G r o - 材 h , 1989 , 9 8 : 2 09 9 N ak 别肚 aur s , M uk ia T, S e on h M . C an d e l a 一 e l a s s Hi hg 一 bir g - h ht e s s I n GaN A/ IG aN D o u bl e 一 h e et or s t ur c t u r e B l u e 一 li hgt - e m it ign D i o d e s [ J] . A P P I hP y s L et , 19 94 , 64 : 16 8 7 10 L u D C , W如g D , W白l l g X , et a l . M e alt 一o r g an i e C he m i c a l 物p o r D e P o s i t i o n G r o , 沈h o f G aN [月 . M a t e r l a l s S e i e cn e an d E n g ine e r ign , 19 9 5 , B 29 : 5 8 1 段 树坤 , 陆大 成 . M O v P E 生 长 G aN 的准热力 学模 型 及 其相 图I J ] . 半导体学报 , 19 97 , 18 : 3 85 12 余庆选 , 励 翠云 , 彭瑞伍 . M O C v D G a l n p 材料 生长 过 程 热力 学及其特性 [J] . 半导体学报 , 19 97 , 18 : 2 53 1 3 H s u C C , y U即 J S , C o he n R, et al . D o Pin g S加 di e s o f G街 , I氏 , P O电 an o m e at ll i e Va P o -r p h as e E Pi at x y【J ] . J A p l P hy s , 19 86 , 5 9 : 3 9 5 14 uY an J S , C h e n C H , C o he n 民et a l . H i hg Q u a li yt G 氏nI 卜 x P (卜0 . 6 5 , 0 . 6 9 ) G r o wt h by O M V P E [J ] . J C yr s alt G ro wt h , 1 9 8 6 , 7 8 : 6 3 P yr o ly s i s E fe e t o f N H , an d P H , o n ht e C o m P o s i t i o n S P a c e s fo r M O V P E G r o wt h o f 111 一 V S e m i c o n d u e t or s LI hC a n g ℃ gn l), L U L’in ) , 恻刃 G uF m i n犷 ) , Z 月月刃G 肠ij ng l) l )M at e r i a l s S e i e n e e an d nE g i n e e r i n g S e h o l , U S T B e ij i n g , B e ij i n g 1 00 0 83 , C h i n a Z )M e t a ll ur g y S e h o l , U S T B e ij i n g , B e ij i n g l 0 0 0 8 3 , C h i n a A B S T R A C T aT k l n g ht e M et a l ~ O r g an i e Va P 0 r P h a s e EP it a x y (M O V P E ) o f G 咖 an d ( G a l , Ixn ) P s e m i e on - d u c t o r s a s e x a m Pl e s , ht e Py r o ly s i s e fe e t o f N H , an d P H , v ap o r s our c e s on ht e e om Po s it ion s Pac e s fo r gr o w in g G aN an d (G a , 一 x l xn ) p e o m p o un d s h a s b e e n sut d i e d . A e c o r d in g t o ht e s iot a t i o n o f N H , an d P H , p y r o l y s i s i n e x - Pe ir m e nt al e on d iit on s , ht e ht e n n o dy n am i c m o ds l s fo r d i fe r e nt P y or ly s i s s t a ut s ar e bu ilt . F u rt h e n n o er , ht e e o m Po s it ion s Pac e s for gr o w i n g 111 一 V s e m i e o n du e for s aer e al e ul aet d a n d Per d i e t e d w iht het ia d o f ht e T h emr o - e a l e s o ft w aer . hT e e o er s Po n d e n e e o f het ht e o er t i c a l an l y s i s w iht het eXP e ir m e n t a 1 d a at in d i e a et s t h a t for ht e ht e mr o d y n am i e an a ly s i s o f M O V P E P r o c e s s o f G aN an d (G a , 一 x l几 ) P s e m i e on d u c t o r s , ht e e a l e u l at i o n an d Per - d i e t i o n mu st b e e o n du e et d un d e r ht e e o n d it i o n s o f ht e e o m Pl et e e qu i lib r i um or ht e e on st r a int e qu ilib ir 切rn b a s e d on het Pr a e t i c a l Py r o ly s i s o f N H 3 an d P H , v ap o r s o ur c e s , T h e an aly s i s o f ht e e o m Pl e t e ht e n n o d y n am i c e ql i - li ibr um 1 5 on ly ap Pli e d to s om e s Pe e iif e t e m P e r a t ur e re g i o n or e e art in e P lt a x y Pro e e s s a ft e r ty Pi e a l P r e讹a tl n e nt o f v a Por s o u r c e s · K E Y W O R D S hte rm o dy n am i e an aly s i s ;V gr o pU v 叩or s o ur e e ; p尹o ly s i s : G aN ; (G a l 一 x l氏)P : M O钟E