is then no difficulty in formation of a vapor b a r r i e r at the silicon surface p h e n o m e n o n can be exowing to the high generation rate of SiF4.

of the reaction products Figures 8 and 9 are, respectively, the equivalent rify this hypothesis, cerkinetic and geometry data for the acetic acid d i l u e n t with N a N Q in order to system. A comparison of Fig. 2 and 8 clearly brings The results are shown in the etching For$our$process:! out the relationship b e t w e e n the two etching systems. rate by the The rates in the two systems obviously must converge gh HF region and in the HF:HNO3:CH3COOH!system$! to identical values along the H F - H N 0 3 axis. In the of catalysis. The reaction ic throughout the entire Winfab$(20:30:50)! H F (49.25 % ) ffect of added catalyst is ere the rate is sufficiently We$need:$15:47:38$ou$6:88:6! atalyst would far exceed reaction is autocatalytic, st more rapidly from the the central portion of the the high degree of attack die relative to the attack HNO3! HF!

WIll/ ~ o///////f I

imens etched in the high ted with the autocatalytic concentration is low, the w activation energy sites, s. F r o m these sites, the t areas as the catalyst w, the catalyst is liberated r o b a b i l i t y that it will be o propagate the reaction. n is very low, the surface isolated pits a n d craters. increases, the density of i l they finally merge into . When the concentration large, the entire surface , and as HF becomes the face becomes smooth and

HC2HsO2 90

80

70

60

Fig. 8. Curves of constant rate of change of die thickness (mils per minute) as a function of etchant composition in the 48% HF70% HNO3-HC2H302 system.

CH3COOH!

50

40

30

20

JO HNO~ (69.51%)

nt areas as the catalyst w, the catalyst is liberated probability that it will be to propagate the reaction. HC2HsO2 90 80 70 60 50 40 30 20 JO HNO~ (69.51%) on is very low, the surface y isolated pits a n d craters. Fig. 8. Curves of constant rate of change of die thickness (mils increases, the density of ! per minute) as a function of etchant composition in the 48% HFFor$our$process: til they finally merge into 70% HF:HNO3:CH3COOH!system$!HNO3-HC2H302 system. n. When the concentration y large, the entire surface k, and as HF becomes the rface becomes smooth and Winfab$(20:30:50)!

e on the two (111) planes What$i$need e d surfaces is greater t h a n ! and much less t h a n u n i t y his can also be correlated the greater dependence of he high HNO~ region with cause of the greater availes, this region should show respect to the center. The e slowly than the center in that the dissipation of the i n g factor governing the HF. In the region of etch tion step ceases to be rate the edges of the specimen ation that these areas will

HF!

HNO3!

CH3COOH!
Fig. 9. Resultant geometry of the etched die as a function of the etchant composition in the 48% HF-70% HC2H~O~ system.

ing itself to interpretation c n a t u r e of the reaction is

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