IEEE TRANSACTIONS ON ELECTRON DEVICES, VOL.

ED-25, NO. 10, OCTOBER 1978 1185 Eds. New York: Academic Press, pp. 251-333. H. C. Nathanson, New directions in nonplanar semiconductor device technology,inZEDM Tech. Dig., pp. 441,1976. R. N. Thomas, J. Guldberg, H. C. Nathanson, and P. R. Malmberg, The mirror matrix tube: A novel light valve for projection displays, ZEEE Trans. Electron Devices, vol. ED-22, no. 9, pp. 765-775, Sept. 1975. R. M. Finne and D.L. Klein A water-amine-complexing agent vol. system for etching silicon, J. Electrochem. SOC., 114, pp. 965-970, Sept. 1967. E. Bassous and E. F. Baran, Fabrication of silicon nozzle arrays for ink jet printing, presented at the Electrochemical Society Fall Meeting, Atlanta, GA, Oct. 1977; alsoinExtendedAbstracts, V O ~ .77-2, pp. 954-955,1977. D.B. Lee, Anisotropic etching of silicon, J. Appl. Phys., vol. 40,no. 11, pp.4569-4574, Oct. 1969. M. J. Declercq, L. Gerzberg, and J. D. Meindl, Optimization of of hydrazine-water solution for anisotropic etching of silicon in integrated circuittechnology, J. Electrochem. SOC.,vol. 122, no. 4 , pp. 545-552, Apr. 1975. R. G. Sweet, High frequency recording with electrostatically deflected ink jets, Rev. Sci. Znstrum., vol. 36, no. 2, pp. 131-136, Feb. 1965. R , G. Sweet,Fluid droplet recorder, U.S. Patent 3 596 275, Jul. 1971. F. J . Kamphoefner,Inkjet printing, ZEEE Trans. Electron Devices, vol. ED-19, no. 4 , pp. 584-593, Apr. 1972. R. D. Carnahan and S. L. Hou, Ink jet technology,ZEEE Trans. Znd. App., vol. IA-13, no. 1, pp. 95-105, Jan./Feb. 1977. J. C. Greenwood, Ethylene diamine-catechol-water mixture shows preferential etching of p-n junction, J. Electrochem. SOC., vol. 116,no. 9,pp. 1325-1326, Sept. 1969. A. Bohg, Ethylenediamine-pyrocatechol-water mixture shows etching anomaly in boron-doped silicon, J. Electrochem. SOC., vol. 118, no. 2, pp. 401-402, Feb, 1971. W. Anacker, E. Bassous, F. F. Fang, R. E. Mundie, and H. N. Yu, Fabrication of multiprobe miniature electrical connector, ZBM Tech. Discl. Bull., vol. 19, no. 1, pp. 372-374, June 1976. E. Bassous and L. Kuhn, Charge electrode array and combinaof manufacture,, U.S. tion for ink jet printingandmethod Patent 4 047 184, Sept. 1977.

[18] E. Bassous, H. H. Taub,and L. Kuhn Ink jet printing nozzle arrays etched in silicon, Appl. Phys. Lett., vol. 31, no. 2, pp. 135-137, July 1977. [19] D.A. Kiewit,Microtool fabricationbyetchpit replication, Rev. Sci. Instrum., vol. 44, no. 12, pp. 1741-1742, Dec. 1973. [20] C. L. Huang and T. Van Duzer, Schottky diodes andother devices on thinsilicon membranes,ZEEE Trans. Electron Devices, vol. ED-23,no.6,pp. 579-583, June 1976. [ 211 - Josephson tunneling throughlocally thinned silicon wafers, , Appl. Phys. Lett., vol. 25, no. 12, pp. 753-756, Dec. 1974. [ 221 T. J. Rodgers and J. D. Meindl, Epitaxial V-groove bipolar integrated circuit process,ZEEE Trans. Electron Devices, vol. ED-20, pp. 226-232, Mar. 1973. [23] T. J. Rodgers and J. D. Meindl, VMOS:High speed TTL compatible MOS logic, ZEEE J. Solid-state Circuits, vol. SC-9, pp. 239-249, Oct. 1974. [24] M. J. Declercq, A new C-MOS technology using anistropic etching of silicon, ZEEE J, Solid-state Circuits, vol. SC-10, no. 4 , pp. 191-197, Aug. 1975. [25] P. Ou-Yang, Double ion implanted V-MOS technology, ZEEE J. Solid-state Circuits, vol. SC-12, no. 1, pp. 3-10, Feb. 1977. [26] K. E. Bean and J. R. Lawson,Application of silicon crystal orientation anisotropic and effects tothecontrol of charge spreading in devices, ZEEE J. Solid-state Circuits, vol. SC-9, no. 3,pp. 111-117, June 1974. [27] K. E. Bean and W. R. Runyan Dielectric isolation: comprehenvol. sive, current and future, J. Electrochem. SOC., 124, no. 1, pp. 5C-l2C, Jan. 1977. I281 H. Guckel, S. Larsen, M. G. Lagally, G. Moore, J. B. Miller, and J. D. Wiley, Electromechanical devices utilizing thin Si diaphragms, Appl. Phys. Lett., vol. 31, no. 9, pp. 618-619, Nov. 1977. gas chromatography system fabricated on a [29] S. C. Terry, A silicon wafer using integrated circuit technology, Ph.D. dissertation, Stanford Univ. Elec. Eng. Dept., 1975. [30] K. E. Peterson, Micromechanical light modulator arrayfabricated on silicon, Appl. Phys. Lett., vol. 31, no. 8, pp. 521-523, Oct. 1977. [31] H. C. Nathanson and J. Guldberg, Topologically structured thin films insemiconductor device operation,in Physics of Thin Films, vol. 8, G. Hass, M. H. Francombe, and R. W. Hoffman,

Anisotropic Etching of Silicon

KENNETH E. BEAN

Abstract-Anisotropic etching of silicon hasbecome an important technology in silicon semiconductor processing duringthe past ten years. It will continue to gain stature and acceptance as standard processing technology in the next few years. Anisotropic etching of (100) orientation silicon is being widely used today and (110) orientation technology is emerging. Thispaper discusses bothorientation-dependent and concentration-dependent etching of (100) and (1 10) silicon. Very exact process control steps may bedesigned into a process by use of (100) anisotropic concentration-dependent and etching. Also, methods of oxide or nitride pin hole detection in (100) silicon are preManuscript received March 16, 1978;revised June 26, 1978. Theauthor is with Texas Instruments, Inc., Central Research Laboratory, Dallas, TX 75 222.

sented. Mask alignments to obtain different etch front termination in both (100) and (110) silicon are shown. Very high packingdensity structures, less than 1 pm, are obtained in the (110) technology, and extremely high etching ratios of greater than 650 tu 1 are obtained in (110) orientation-dependent etching. Some of the many applications for anisotropic and concentration-dependent etching are described.

ORIENTATION-DEPENDENT, ETCHING ET CHEMICAL ETCHING hasbeen used in silicon semiconductor processing since its beginning inthe early 1950s. Isotropic etches, Le., etches etch that in all crystalographic direction at the same rate, consisting of hydro-

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and 16. This alignment is also parallel and perpendicular with the (1 10) direction or the flat on the (100) slice. This etch ETCHES CHARACTERISTICS COMPOSITION RATE REhZARKS AND attacks oxide at -28 A/min, however, Si3N4 is not measur. ~. .. - HNO3 - H A-C5 p l M I N 11111 RT PLANAR ETCH ETCH UNIFORMITY HF ably attacked even ater 5-hours etchingat 80C. -8% -75% -17% 1 Anotherorientation-dependentetchthatmay beused for 1-3-10 ETCHES P * OR N t 1 HNO3 HAC HF i - 3 p 1 M I N 11OOl RT (100) direction etching to advantage is ethylenediamine SILICON , "STOPS" AT P- OR N' 1 1 3 10 I 255 cm3, pyrocatechol 45 g,andwater120cm3,hereafter 1 0 1 ODE 13 ETCHES [loo] -100 I KOH - N O R -M1A LM I N pl AT 80C referred to as EDA [7] , [9] -[11] , [21] . This solution etches X [ l] I l DIRECTIONPROPANOLHz0IN (1001 SILICON STOPS AT P" INTERFAC 1 (100) silicon at 1.1 pm/min at 100C and SiOz at -8 A/rnin. B p I M I N AT 80C The slow etch rate of SiOz and the non-sodium or potassium 1 IN (1101 SILICON nature of this etch makes it desirable for polysilicon etching in EIHYLENEDIORIENTATION DEETHYLENEDI1 - 1 . l pIM]I N AT 1W"C I AMINE PENDENT AND , AMINE - CATECHOL - I N [ W STOPS MOS-typedeviceprocessing. This etch is also concentration AT ' ETCHING Pit INTERCONCENTRATION FACE. , $?DRAZ,NEl DEPENDENT VERY SLOW and/or type sensitive and stops or greatly reduces in etch rate ETCHING OF Si02 I I at a pt interface or junction. This etch may also be used for (110) direction etching, hydrazine may also be added t o this fluoric, nitric, and aceticacid (HF, HN03,and CH300H) were solution for faster etching. Another etch solution which very is used for etching and chemically polishing in the early w:9rk orientation-dependentinthe (1 10) directionetching is po[ l ] -141. In the more recent past, people have become inter- tassium hydroxide and water (KOH -35 percent by weight, ested in anisotropic or orientation-dependent etches [5] .-I71 and HzO) at 80C. Thissolutionetches silicon six hundred (ODE). This paper will discuss primarily wet chemical, oricntimes faster in the (1IO) direction than in the (1 11) direction tation-dependent, and concentration- dependent etching; h sw- when the mask is properly aligned with the trace of the (1 11 ) ever, vaporphase andplasmaorientation-dependentetching plane at the (110) surface or 35.26" off from the (110) flat. are also of current interest and many of the same masking ;!nd (Not parallel and perpendicular to the (1 10) flat or direction alignment technologies apply. We will describe etch solutioos, in this case [20] .) The (1 10) silicon etch rate is -0.8 pmlmin masking materials, mask alignments, and impurity concenm- and the SiOz etch rate is -30 A/min. tion etch dependence for both (100) and (1 10) silicon orier [.aSiliconbelongs tothediamondcubic crystalstructure. In tionis. Some applications for each orientation will be described. the cubic structure the crystalographic directions are perpendicular to the crystal planes. There are several low-index Etches and Masks planes that we may choose to work on in this diamond cubic Table I givessomeof theetches used in both planar End structure. Fig. 1 shows examples of some of these planes and orientation-dependentetching. Planar etch is anetch con- their position the in cubic structure. Numbers three, one, sisting of hydrofluoric, nitric, and acetic acid (HF 8 percent, and sevenare thethreeindexplanesmostcommonly used H N 0 3 75 percent, CH300H 17 percent).Thissoluton for silicon device processing. Fig. 2 shows one of each of the etches silicon atabout 5 pm/min at25C.Theetchrat( is low-index planes in the cube, that is, the (loo), the (1 lo), and approximatelyequalin all crystalographicdirections as 1he the(111). One of theimportant parametersinorientationname planar indicates. The ratios of the constituents of plaa1,ar dependent etching of silicon is the atomic lattice packing etch may be altered to change the etch ratedrastically. ]:':x density and available bondsinthecrystalographicplane. In example "B" etch is a mixture consistingof1 part HF, Fig. 3 we showphotographsofthe silicon diamondcubic parts H N 0 3 , and 15 parts CH300H which etches (1 11) silicon structure model taken from three different crystal directions. very slowly, -0.15 pm/min, and (100) at -0.20 pm/min at The (1 11) direction shows a very high atomic packing density 25C (approximately the rate of planar). in the (1 11) plane. The (100) direction photo is taken of the Another etch made up of these same chemicals is Dash etch same model but moved around 54.75" from the (1 11 ) direc[3], [6], [8]. This etch is somewhatorientation-dependent tion, so we are nowlooking at a(100)plane.It isreadily and is used for crystal defect delineation or definition in (1 1 i ) evident thattheatomic packingdensity is considerably less silicon. Itetches p n or silicon in the (100) direction :kt dense. The (110) direction photo is taken by moving around original (111) direction.Theatomicpacking -1300 A/min, at 25"C, and at 46 A/min in the (1 11)dircrc- 90"fromthe tion at this same temperature. However, this etch also etckas density is very low in this plane when compared to the { 1 11} heavily doped silicon (p+- or n+-type greater than 5 X 10") plane. From this information one would expect that the etch be considermuch faster (-2.5 pm) than lightly doped p- or n-type silicol. rate, or epitaxial deposition growth rate, would ably faster in the (1 10) direction than in the (100) direction (See Table I.) Therefore, it becomes concentration-dependeru:. An even moreorientation-dependentetch used for etchi:ig and even more so than in the ( 11 1) direction. When we examine the crystal projection of the silicon (100) (100) silicon is 250-g potassium hydroxide, 200-g norm1 propanol,and800-gdeionizedwater [9]. This etch can :le plane, Fig. 4, wesee thatthe { 100) surfacehasfour-fold { 11 1} masked by photoresist for shallow 25C etching or by use I f symmetry. That is, the high atomic packing density : N planes are equaldistance outfromthe (100) surfaceplane SiOz or Si3N4 for deep (>20 pm) etching at 80C. The etch rate in the (100) direction is at least one hundred times faslcr at equal angles and they are 90" to each other. Also we can than in the (1 1) direction if the mask is properly aligned wi t h determine that the { 1 11} planes are intersecting the {loo} 1 the trace of the ( 11 1) plane at the (100) surface, see Figs. . 5 plane at a rather steep angle, which is 54.74", and that they
.. -. . .

TABLE I CHEMICAL ETCHING OF SILICON

'
1

&

BEAN: ANISOTROPIC ETCHING O F SILICON

PATTERN OPENED IN OXIDE

1187

Fig. 1. Crystalography of silicon substrate orientations,

11101 FLAT
SECTION THROUGH WINDOW AFTER ETCHING

Fig. 5 . Mask alignment on (100) silicon.

Fig. 2. Low crystalographic index planes of silicon.

SEk1 CROSSECTIONAL V I E W (1001 D l ETCH

Fig. 6. Top view and cross-sectional view of (100) ODE silicon.

<Ill> ClW>

<110>

Fig. 3. Model showing three low-index directions of silicon.

io0

(1001 ODE, SEM Fig. 7. ODE etch pit in (100) silicon.

are in (1 10) directions. (See thefour { 110) planesat the periphery of the projection. Theseare 90' to the (100) surface plane.) When we grow an oxide, or deposit a silicon nitride masking film on the {loo} silicon slices and then align a mask parallel and/or perpendicular to these 110) directions (as indicated in

, '

Fig. 5, as instandardphotolithographicprocessing, ) wecan open up narrow lines, through the mask material, which are aligned parallel with trace the of the high atomic packed { 11 1) planes. Whenweplace these slices in an orientationdependent etch such as KOH, normal propanol, and HzO, the etching will proceed in the ( 100) direction (into the slice) until the etch front hits the (11 1) planes, intersecting the (100) plane at the edge of the mask opening, and .then the etching will stop as in Fig. 6. Also see data in Figs. 13 and 14. The etch depth to oxide opening width ratio 0.707. That is if we is open an oxide pattern line 10 pm wide it will etch 7.07 pm deepandthenforpracticalpurposesstopetching.Due to this effect one can use ODE on (100) silicon as a method for determining pin holedensityinoxidefilms. When one uses ethylenediaminepyrocatecholandwater (EDA) (255 cm', 54 g, 120 cm3, respectively)at100C theetchfront will propagateintothe(100) silicon to form a perfect square topped inverted pyramid, through the pin hole (see Fig. 7). If

1188

TRANSACI'IONS IEEE

OCTOBERED-25, ON ELECTRON 1918 NO. VOL. 10, DEVICES,

\-,

\-I

Fig. 8. (a) (loo), ODE, 2040X 65" SEM of 10-pm squares on 20+m centers. (b) (100) ODE 1240X 65" SEM of 10-pm squares containing mask oxide.

(a)

(id

180 X SEM

1.2W X 8 SEM 0 '

Fig. 9. Corner undercutting in (100) silicon versus ODE depth. pm deep. (b) 54 pm deep.

(a11 2 3

Fig. 12. Corner faceting in (100) ODE, 50 pm deep.

1.91 4,70 9.35 13.49 16.38 20.57 24.13 26.87 30.78 33.50 5
10

5 10
1s

23
30

34 38

44
49

54

15

20

25

30 40

35

Fig. 10. Corner undercutting versus ODE depth in (100) silicon.

one uses a square window frame pattern opened in the oxide or nitride mask and the same etch conditions, a square bassd pyramid structure can be etched as in Fig. 8(a) and (b). Fig. 8(a) was etched using a thin 1000-A oxide mask and 8-1rsn etch time in EDA as above. In this case, the thin oxide mark is leftintactonthe pyramids. In Fig. 8(b), additiorml an 30-s etch in planar etch was used to point the pyramids a : d liftoffthe oxide. The pyramids are 8 pm high, and have 10 pm/square bases on 20-pm centers. In the case where m e wishes to etch V-grooves for isolation purposes or for VMYN structures, edge undercutting of the mask is negligible, however,cornerundercuttingmaybecomeaproblem in deep, >20pm,etchdepths forisolationstructures [ 121-[14 1. Fig. 9 shows the effect of corner undercutting on the relativc1.y fast etch {331} planes, which are exposed on outside (convex) corners in masked arrays. Corner undercutting does not 0cc:I.m at inside (concave) corners. In Fig. 9 it can be seen that correr undercutting is related toetchdepth. Fig. 10plotsthis :elationshipofcornerundercutting toetchdepthsfor {lOill} silicon using the KOH, propanol, H20 etchat 8OoC. Frcm this data one can design corner compensation into the mark t o preventthefacetedor rounded corners. Fig. 11shows an example wherein mask corner compensation was used to p w

duce square corners in arrays that require 50-pm-deep etching. Notethecornercompensationandoxidemaskpatternprojecting out into space above the ODE V-groove. With corner compensation, underetching will leave a tip of silicon sticking out at each corner, see Fig. 13(a), and overetching of the designed compensation-to-depth ratio will, of course, undercut the corners. Fig. 12 is a 180X SEM of a { 100) ODE silicon slice etched 50 pm deep without corner compensation of the mask.Notethe (331 } faceting or roundingoftheoutside corners. The double four-fold symmetry of the {33 1 } planes in (310) directions, see Fig. 4, is evident in the corner faceting of this pattern.Note the octagonshapeatthe topof the smaller mesas. These (331 } planes intersect the { 100) silicon surface at an angle of 46.5",which may be advantageously used in some cases, and will be further discussed later. Also note the exact crystalographically sharp 90" corners at the inside corners of the array. Fig. 12 also shows a higher magnification view of these (331) facets. Again note the exact crystalographic structure of the ODE front. As was previously mentioned, the ODE stops when the etch depth reaches the depth at which the two { 11 l } planes at the edge of the mask opening intersect. If the mask is properly aligned the with {I 10) direction no undercuttingoccurs along the mask edges (only at convex corners). Fig. 13 shows evidence of thisstatement. Fig. 13(a)showsa (100) silicon slice with a corner compensated oxide mask. This mask has oxide open lines 97.5 pm wide at the silicon-oxide interface. After etching 38 min at 80C the etch depth measured 38 pm deep and the width opening at the silicon-oxide interface measured 97.5 pm.Notethetip of siliconprojecting out under the compensated corner oxide. (The corner compensation was designed for 50-pm etch depth.) The slices were placed back in the ODE for another 30 min at 80"C, thus giving a total ODE time of 68 min. At this time the etch depth measured 69 pmdeepand the linewidthopeningatthesilicon-oxide interface measured 97.5 pm, see Fig. 13(b), indicating no undercutting of the oxide mask. The ODE should "V" or bot-

BEAN: ANISOTROPIC ETCHING OF SILICON

TOP FOCUS

1189

BOTTOM FOCUS

(a)

Ib)

Fig. 15. Undercutting versus mask alignment accuracy in (100) (a) 1.5' off alignment. (b) 3.9" off alignment.
1 0

ODE.

9
- 8

(1WI ODE 68 "IN. 80 C . 69pihl DEEP, WIDTH AT OXIDE M A S K

97 5pihI

g 7 2 6

Fig. 13. (100) ODE, 38- and 68-min etching.

TOP FOCUS BOi7OM FOCUS

5 5 = 4
= 2

g3
1

DEGREES OFF ALIGNMENT

Fig. 16. Undercutting versus alignment accuracy.

(IWI ODE. 98 MIN. BO C. 69.9pM DEEP, WIDTH AT OXIDE MASK

97.5piM

Fig. 14. (100) ODE, 98-min etching.

tom out at this depth and time. That is 97.5 X 0.707 = 68.9. The slices were again placed back into the ODE for an additional 30 min.Afterthisadditional30-minetch,thedepth measured 69.9 pm and the linewidth opening at the siliconoxide interface again measured 97.5 pm, indicating no undercutting of the oxide mask even after 48-min overetching. The total etch time was 98 min. The complete lack of undercutting indicates the etch stopping ability of the (1 11) planes when the(100) slice is properlyaligned.Fig. 14 shows the ODE slice after a total of 98-min etching. Note in Fig. 13(b) thefaceting of thecornersunderthecornercompensation due t o overetchingfor 18 min.Thecompensation was designedfor50-pm etch depth. Also note the "V" bottom in the bottom focus photo of Fig. 13(b) indicating the completion of the ODE. A replica of the trace of the { 1 11) planes can be seen inthecornercompensationoxideinbothFig, 13(b) and Fig.14.Thisreplica is due t o a change inmask oxide thickness, and shows that the ( 11 1) planes blocked the corner undercutting for some period of time before breaking down to allow corner undercutting, or faceting, to the faster etching (331) planes. The importance of properalignment cannot be overemphasized in the use or orientation-dependent etching. If amaskis aligned offthedesiredcrystalographic direction undercutting will occur until the etch front reaches the slow etch { 11 1) planes.This will occurinaseries of plate-like steps, see Kendall [15]. Fig. 15 shows a top view of two (100) silicon mesas with corner compensated oxide mask, ODE 50 ,urn deep. Undercutting can be detected as a function of mask alignment. Measurements were made from slices misoriented from 1" t o 7" and ODE 50 pm deep using (100) ODE at 80C. The dataareplottedin Fig.16. As inthe case of

la1

ib)

Fig. 17. ODE of (100) silicon. (a)(310)alignment. (b)(llO)alignment.

Kendall, for (1 10) silicon, the (100) dataalso give a linear plot ofundercutting versus degrees offalignment.Note also the plot projectsthroughzeroindicating no undercuttingfora properly aligned mask on (100) silicon. The W/D (undercut to depth) in this case is 0.10 at 4" off orientation whereas the U/D for (1 10) silicon is 0.10 at 3.5" off orientation. This indicatesaslightly less stringentdependence on alignment accuracy for { 100) silicon. Ifwe reexamine the silicon crystal structure projected in Fig. 4 we see the double four-fold symmetry of the (3311 planes, mentioned and identified in the discussion of Fig. 12. These planes have been identified as the prevalent, fast-etching, corner-undercutting planes when using either KOH, propenal and water, or EDA in our work. Others have identifiedthecorner facetingplanes as (221) planes when etching with EDA [7] , [16] , These relatively low (46') angles, with respect to the (1 00) planes, may be advantageously used in cases wherein one wished to run metallization up and down these planes [ 171. Fig. 17 shows examples of two (100) silicon slices ODE at the same time in the same solution and having the same mask pattern. Slice in Fig. 17(a) had the mask pattern aligned parallel with the {3lO) direction, which gives etch termination on the 46" (331) planes. Slice in Fig, 17@) had the mask pattern aligned parallel with the normally used (1 10)direction. The mask did not have corner compensation; however, notethe perfect90"cornersinthe (310) aligned slice and the corner undercutting on the (110) aligned slice. It should be pointed out that edge undercutting is much greater in the (310) directionalignment. 'The ratio is 18+munder-

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IEEE TRANSj,rCTIONS ON ELECTRON DEVICES, VOL. ED-25, NO.

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(a]

D l ARRAY M A S K

fbl ODE iloOl 53 p m DEEP

Fig. 18. Effect of mask corner compensation on ODE and ODD

ORIENTATION DEPENDENT DEPOSITION ORIENTATION IlMI 1K X DEPENDENT DEPOSITION

!lWl 2.5K X

Fig. 20. Orientation-dependent deposition on (100) silicon through circular oxide mask openings. lOOOX and 2500X magnification.

(a)

AFTER D ! (POLY POLISHBACK)

fbl

AFTER E P I ON D!

Fig. 19. Effect of mask corner compensation of ODE and ODD.

cutting per 25-pm etch depth. There is no corner undercutt:rng in the (310) aligned slice, due to the fact that the faster etl:!ning (331) planes are now the etch terminating sides, or ma ;king edge. The effects of orientation-dependent etching, mrak etch corner compensation, orientation-dependent and depositim in graphicallydisplayedin Figs. 18 and 19. Fig. 18(a) i~ a maskarray for dielectricisolation processing [12],[14]of aseven-elementarraywhereineachelementis dielectricaly isolated from its neighboring element. The eleven narrcw rectangles above the seven-element array are thickness indic ators designed intoeach circuitbar. These indicators revtd the thickness of the single-crystal layer in each finishedcirc1,it or array [ 131, [ 141. At the left end of the thickness indicxtors there are two alignment squares, one with and one wit.% out corner compensation. These squares are initially the sa11113 size. After ODE, 53 pm deep, uncompensated the com:r square has etched to an octagonal shape, consisting of eiglll: {331} planes as sides. (SeeFig.18(b).) Notethe large difference in size or surface area at this point in processing. TI c undercutting of the masking oxide is evident in this photc~. graph. Fig. 19 shows the left side of this same array after tftr slice has completed dielectric isolation processing. The moa +I have been filled with polycrystalline silicon, the slice invertled and ground and polished back t o the isolated silicon island:;., Note the near perfect square from the compensated mask aree and the near perfect octagon from the uncompensated mas c area. Also notethe first two thickness indicators showing through. (Fig. 19(a) is looking at the back side of the slic: with respect to Fig. 18(a).) Fig.19(b)showstheeffect 01 Orientation-dependent deposition of silicon after the slice, as in Fig. 19(a), has had an epitaxial deposition which is actualll:! simultaneous deposition of single- and polycrystal silicon. Tht: two squares are the compensated and uncompensated squara: areas. The octagon, (331) plane bounded, figure has growr. back t o a near perfect square bounded by { 111 } planes. Note the (100) stacking in mask fault the corner compensatec square. Another example 0 : 1 orientation-dependent depositior: [13],[18], [ 191 is shownin Fig. 20. These nearperfecl squares are grown through an oxide mask with 5-pm-diameter

Fig. 21.Standard (110) crystalprojectionforafacecenteredcubic crystal with { 111) and {22 1) planes designated.

circles, open for silicon nucleation. The 5-pm-diameter circles are on 25-pm centers; therefore, one can see the lateral spreading effect of the (100) oriented epitaxial deposition. The final width of the "Epi Top" in this case is 18 ,um. The epitaxial linear growth is -6.5 pm on each side of the original 5-pmdiameter mask opening.

(1 10) Orientation-Dependent Etching

When we examine the crystal projection, Fig. 21, of the very open lattice (1 10) direction of silicon, shown in Fig. 3, we find that the high packing density { 1 11} planes are now 90' to the (1 10) surface plane, however, they are no longer 90' to each other. Thisindicatesthat we can etch vertical moatswith straight wall (1 11} side termination. We have found that we have a >600 to 1 etching ratio in the (1 10) to (1 11direction ) [I41 -[19]. This means that we can etch very narrow, for example, 0.6-pm wide, moats on very tight packing densities, for example, 1 pm or less center to center, straight down into or even completely through a (1 IO) oriented silicon slice. In this (110) mirror image symmetry we also have two relative lowangle (1 11} planes intersecting the (1 10) surface at 35.26'.

BEAN: ANISOTROPIC ETCHING O F SILICON

1191

11101, ODE, 570X.

85' SEM

Fig. 22. 5000X 80' SEM of (110) ODE silicon 0.6-pm ridges on 1.2-um centers.

Fig. 25. 570X 85" SEM pointed ridges on l@pm centers, (110) ODE.

-I

l-

(1101 ODE, 11.5KX. 85 $EM

Fig. 26. 11 500X 85' SEM pointed ridge.

5WX

10, owx

Fig. 23. lOOOX, 5000X, and10 OOOX SEM's of(110) ODE silicon. 80-pm etch depth, 5-pm ridges on 10-pm centers.

Fig. 27. 160X 60" SEM cross-sectional and top view of (110) silicon slice, ODE from top and bottom surface simultaneously.

Fig. 24. 240x

80' SEM of 10" off (110) ODE silicon. 5-pm ridges on

10-pm centers, 160 pm deep.

The effect of these will be seen and discussed later. (See Fig. 22.) Fig. 22 is a 500X, 80' SEM of a cleaved (cross-sectional) (1 IO) silicon slice that was etched using 50 percent KOH, 50 percent D.I. wateretchat 80'C. The oxide mask was opened by e-beam lithography and had 0.6ym-wide openings on 1.2ym centers.Someundercutting,due to aslight misalignment, is evident at the oxide mask surface. We routinely obtain etch ratios greater than 600 to 1 using this etch system, that is etching 600 pn deep in the(1IO) direction while undercutting less than 1 pm in the ( 111) direction. See Fig. 23, Fig. 23 is a series of three SEM's of a (1 10) ODE cross section. The etchdepth is 80 pm,themaskpattern is 5-pm-wide moats open on 10-pm centers. The top SEMis at IOOOX magnification. Note the low-angle (1 11) planes at the bottom of the moats. The lower left SEM is of the same structure at 5000X magnification and the lower rightSEM is at 10 OOOX magnification. The original 6000-a-thick oxide mask is readily seen at the 5 and 10 thousand magnifications.Thesestructuresmay be tilted at any angle by simply cutting the (1 10) silicon slice

at the desired angle off the (110) direction. Fig. 24 is a 240X, 80' SEM cross-sectional view of an ODE (1 10) slice that was sawed 10' off the (1 10) plane. These very narrow ridges can be diffused oxidized and b,y normal silicon semiconductor processing. may They also be pointed to extremely sharp points as is shown in Figs. 25 and 26. This is accomplished by etchinginDash-typeetchforapproximately 10 min after moat etch is completed. Fig. 25 is a SEM, cross-sectional view, at 570X magnification. When an array such as this is pointed, the top (1 10) surface becomes a black body, with no surface reflection. Fig. 26 is an eleven and one half thousand X (1 1.5 thousand X ) SEM of one of these pointed ridges. Even at this magnification it is difficult to estimate a radius of curvature. Very fine, high density X-Y structures, or sieves, can be made by etching the (1 10) slice with masks aligned with the 90" (1 11) traces on both sides (top and bottom) of the slice. This pattern forms a rhombus with 109.47' obtuse angles. Fig. 27 is a 60' SEM showing both top and cross-sectional views of a (1 10) silicon slice, etched from both sides simultaneously. A quadrant wascleaved out of the slice for photographic purposes. Fig. 28 is a 500X magnification, SEM, of the top surface of the (110) slice etched from both sides simultaneously. The slice was 269.2pm(10.6 mils) thick.Themaskopens 5-pm-wide moats on 20-pm centers on both sides of the slice, resulting in 5 pm X 5 pm rhombic openings when etched to completion. Fig. 29 is a2000X SEM ofthestructure. This structure offers new possibilities in electrical X-Y addressing, and optical mechanical designs.Inan experiment, a rhombic window frame maskwas purposely aligned 109" off the proper

1192
APERTURES - 5 p ON 20 p CENTERS m m * V I E W I N G ANGLE - 0 DEGREES *SLICETHICKNESS - 10.6 WlLS
0

SOME I\PPLIC/ITIOI\IS FCR

_____
_____
ELECTRONIC VERTICAL PRINTER WAVE SENS DiTECTOIIS IR PLANAR CRCSSPOlldTS IS0 PLANAR POLY V NtOS J FET ARRAYS HIGH ilOOl

-.:filLI: I[ AND ( ! 10) A%lSOTROPI(.E.r(:HING Sxr::covI)E:VCE I ~ , E S L ; ~ G F

(1oc)

IPI

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R A D l A T l O h HARDENED C I R I X IH I S i G

JCT SOLAR C i L L

STOR hIETA.LiZATION 7EMPL411:S VALUE. CAPACITtIR!, COLI.IP114I)RI

D l IROCESS THICKNESS0PTII:AL INDICATOR

Fig. 28. 5OOX SEM, (110) ODE aperture grid, apertures 5 prn X 5ttm on 20-pm centers etched through 270-pm-thick slice.

SOLID STATETRANSDUCER PRESSURE BLAC< BODIES

-_____

SOLAR CELL ANTI-REFI.ECTING SURFACE

____

Fig. 29. 2000X SEM (110) ODE aperture grid. 5 pm on 20-pm cein . x s etched through 270-pm-thick slice.

are 4 j off a normal (1 10) flat, see Fig. 21, arid may be used !0 for vertical etching of 90 corner structure (sq~mes,rectangler;, shapes, e:tc.) :in (1 10) crilicaa. A sqpare, 9 Icormr 0 pattern wasaligned in this manner and etched 24 ~.un deep. Fig. 31 shows the resulting 90 comersafter etching,, The undercutting to dep1:h ratio is 18 to 24 pnn, :tpgwalximatel.:y the same as that of the (310) direction alignmlenlt on. the: (1001) silicon surface. Again perfect 90 corners areclbtainedl without mask corner compensation. Some of the many appli~atio~ns for anisotropic etching, in semiconductor device processing are listed in Tlhble I.[. T h i s is only a partial listing a:nd a small beginning in the use of Ithis versatile technology.
1 ;

ACKNOWLE:DGMENT
{110} SILICONO.D.E. ETCHED 24pm. DEEP RHOhlBUS PATTERN ALIGNED 35.26 OFF i l l 0 1 FLAT ACCUTE ANGLE UNDERCUT MEASUREDSIDE 76 FROU {IIO}
OF 90

10-90

FACET

ANGLE TO BE 45 OFF IliGl FLAT

SURFACE

Fig. 30. (110) silicon ODE 24 pm deep. Rhombuspattern aligned 35.26 off (110) flat. Acute angle undercut to 90 crystal facet.

The author wishes t o thank his fellow workers, J. Powell, L. Webb, R. Staring, I). Yeakley, B. Housevvright, T. Powell, Dorothy Splawn, and W. Runyan for their many contributions to this work. Also special thanks to W. Rlunyan andHettie Smith, Emily Appersan, M. White,andR.Steinforcritique and preparation of the .manuscript. REFERE:NCES
D. R. Turner, Electropolishing of silicon m hydrofluoric ,acid i vol. solutions, J. Electrochem. SOC., 105, pp. 402-4.08, 1958. R. R. Stead (Texas Instruments Incorporated.), Etching of semiconductor materials, U.S. Patent 2 871 110, Jan. 1959; U.S. Patent 2 927 011, Mar. 1960; U.S. Patent 2 973 25:3, Feb. 1961. B. Schwartz and H. Robbin, Chemical etching of silicon, Part I, The systemHF, HNO3, H z 0 and HC2H302, J. Electrochem. Soc., vol. 106, no. 6, pp. 505-508, 1959; Part 11, J. Electrochem. Soc., vol. 107, no. 2, pp. 108-111, 1960; Part 111, J. Electrochew. Soc., vol. 108, no. 4,pp. 365-372, 1961. W. C. Dash, Copper precipitation ondislocation in silicon, J. Appl. Phys., V O ~ .27, pp. 1193-1195, 1956. J. M. Crishal and A. L. Harrington, A selective etch for elemental silicon, Electrochem. SOC. Extended Abstract #(SpringMeeting, 1962, Los Angeles, CA), Abstr. no. 89. R. M. Finne and D. L. Klein, A water amine complexing agent system for etching silicon, E.C.S. J., vol. 114, no. 9, Sept. 1967. D. B. Lee, Anisotropic etching- of silicon, J. Appl. Phys., vol. .40, no. 1, Oct. 1969. H. Muraoka and T. Y.Sumitomo, Controlled Pre.ferentia1Etching Technology, in Semiconductor-Silicon 1973 (Electrochemical Society, H.R. Huff and R. R. Burgess, Eds.). J. B. Price, Anisotropic etching of silicon with KOH-Hz0 isopropyl alcohol, in ECS Semiconductor Silicon 1973, pp. 339-353. [lo1 J. C. Greenwood, Zbid., vol. 116, no. 9, Sept. 1969. 1111 A. Bogh,Zbid., vol. 118, no. 2, Feb. 1971. [12] U. S. Davidson and F. Lee, Dielectric isolated integrated circuit

{IlG} SILICON O.O.E. ETCHED 2 4 p m DEEP

ALIGNED 45 OFF OF THE ilDi FLAT

9Y CORNERS

NOMASKCOMPENSATION

UNDERCUTTING W A S 17.8 urn. ETCH TERMINATION ON

{22$

INTERSECTS THE 110 SURFACE AT 76

i\

221 PLANES

Fig. 31. (110) silicon ODE 24 pm deep.Square pattern aligned 45 off (110) flat. 90 corners with no mask corner compensation, etch termination on (221) planes.

alignment of the sides with the { 1 11) traces at the (1 10) surface. The resulting etchedstructurehadundercutting at all four corners. (See Fig. 30.) However, it was observed that the acute angle ofthe masked structureundercut to a palit of planes that are 90 to each other and 76 from the (1 10) ,mrface plane. These planeswereidentified as (221 } planesthat

IEEE TRANSACTIONS ON ELECTRON DEVICES,

VOL. ED-25, NO. 10, OCTOBER 1978

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[ 131

[ 141

[15]
[ 161

substrate processes, Proc. IEEE, vol. 57, no. 9, pp. 1532-1537, Sept. 1969. K. E. Bean and P. S. Gleim, The influence of crystal orientation on silicon semiconductor processing, Proc. IEEE, vol. 57, no. 9, pp. 1469-1476, Sept. 1969. K. E. Bean and W. R. Runyan, Dielectric isolation: Comprehensive currentfuture. Electrochem. Soc. J., vol. 124, no. 1. _ _ . PP. 5C-12C, Jan. 1977. D. L. Kendall, Appl. Phys. Lett., vol. 26, no. 4, p. 195, Feb. 15, 1975. M. J. Declercq, A new CMOS technology using anisotropic etching of silicon, IEEE J. Solid-state Circuits, vol. SC-10, no. 4, pp. 191-197, Aug. 1975.

[17] K. E. Bean, J. S. Crabbe, G. Hoffman, and F. D. Malone, An improved radiation hardened JFET array, inSemiconductor Silicon 1973 (Electrochem. Soc.), H. R. Huff and R. R. Burgess, Eds. [ 181 R. K. Smeltzer, D. L. Kendall, and G . L. Varnell, Vertical multiple junction solar cell fabrication, in Conf. Rec. Tenth IEEE Photovoltaic Specialists Conf.,p. 194, 1973. [ 191 K. E. Bean, R. L. Yeakley, and T. K. Powell, Orientation dependent etching and deposition of silicon, in ECS Extended Abstracts Spring Meet. (May 1974), vol. 71-1. [20] D. F. Weirauch, J. Appl. Phys., vol. 46, p. 1478, 1975. [21] E. Bassous and E. F. Baran, J. Electroch. Soc., vol. 125, no. 8, Aug. 1978.

.I.

Holographic Interference Lithography for Integrated Optics

WILLIE W. NG, CHI-SHAIN HONG,
AND

AMNON YARIV, FELLOW, JEEE

Absfract-In this paper, some of our recent work in the use of holo- various techniques of lithography, material removal, and degraphic interferencelithographyand variousmaterialremoval tech- position in the fabrication of devices, we will only sketch the niques to corrugate thin-film optical waveguides are reviewed. The basic principles of designing periodicthin-film waveguides. specific applications of these periodicthin-film devices in the distributed Fordetails regarding thetheoreticalaspects, the interested feedback and distributed Bragg reflector semiconductor laser, and as output grating couplers, are described. Recent results in the use and reader is referred to [ 1 3 . This paper attempts to supplement fabrication of chirped and curved-line gratings are also summarized. [ l ] , especially in the experimental aspects.

I. INTRODUCTION N INTEGRATED OPTICS we are interested in investigating the possibilities of incorporating optical components in thinfilm waveguides. The diffraction grating and the geodesic lens are examples in which thin-film technology and microfabricationtechniques have made possible theirincorporationinto guided wave configurations.The gratingsarefabricated by corrugating an interface of the waveguiding layer as shown in Fig. l(a). Since, in most cases, the period of the corrugations required is of the order of a micrometer or less, conventional optical photolithographic techniques cannot be used for writing the gratinglines.Instead, the gratingmasks have to be generated either by electron-beam lithography or holographic interference techniques. The latter is a maskless technique that records the interference fringes of two collimated interfering laser beams. In this paper we describe the state of the art of this technique its and application to some optoelectronic devices. Since this Special Issue is devoted mostly to a review of the
Manuscript received February 29, 1978; revised June 15,1978. This work was supported by the Air Force Office of Scientific Research and the National Science Foundation. The authors are with California Institute of Technology, Pasadena, CA 91125.

In Section I11 we describe in detail the fabrication of small period gratings by holographic interference. In Section IV we will describe thedistributedfeedbacksemiconductor (DFB) and distributed Bragg reflector (DBR.) lasers. Such lasers utilize Bragg reflection as thefeedbackmechanismfor laser oscillation and thus eliminate the necessity of terminating the semiconductor laser cavity at one of the cleavage planes of the GaAs substrate. The gratings also provide wavelength selectivity and stability [2] for the multiplexing of optical signals in opticalcommunication.Section V describes the use ofionmilling for the fabrication of blazed gratings that can be used as output couplers for thin-film waveguides. And finally, in the last section, we describe some of our work in the use of curved wavefronts to generategratinglineswitha variable period [3] (chirped gratings) and novel curved line gratings that have focusing properties. The use of the former for wavelength demultiplexing has been demonstrated [LC], [5]. 11. WAVE COUPLING CORRUGATED IN WAVEGUIDES The caseofBragg reflection by a corrugated waveguide is shown in Fig. l(b). The perturbation of the thin-film waveguide by corrugations the causes a contradirectional wave A ( z )e i P z , to be generated from the incident wave B ( z ) e-@. The effectiveness of coupling is derived from a pair of coupled mode equations [ 6 ] and is characterized by a coupling parame-

0018-9383/78/1000-1993$00.75 0 1978 IEEE