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Capacitance-voltage profiling and the characterisation of III-V semiconductors using electrolyte barriers

This article has been downloaded from IOPscience. Please scroll down to see the full text article. 1986 Semicond. Sci. Technol. 1 7 (http://iopscience.iop.org/0268-1242/1/1/002) View the table of contents for this issue, or go to the journal homepage for more

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Sernicond. Sci. Technol.1 (1986) 7-27. Printed inGreat Britain

P Blood
Philips Research Laboratories, Redhill, Surrey RH1 5HA, UK Received 2 1 October 1985 Abstract. This article is a personal review of the principles, capabilities, limitations and potential of the technique of electrochemical capacitance-voltage (C-V) carrier concentration profiling of compound semiconductors and the associated technique of photovoltage absorption spectroscopy. The profiling technique was developed by Ambridge and co-workers to overcome the depth limitation in depletion C-Vprofiling by using an electrolyte barrier to measure the carrier density and to etch the material in a controlled electrolytic process. The electrolyte also provides a transparent barrier which facilitates observation absorption of spectra, hence providing the added capability of band-gap profiling. In this article the basic principles of C-V profiling are summarised, we analyse the balance between measurement accuracy and instrumental depth resolution, and consider the effect of series resistance. In reviewing the principlesof electrochemical C-V profiling, we pay particular attention to the electrolyte (Helmholtz) capacitance, the high electrolyte resistanceand the definition contact of area. In considering these problems, and those of depth resolution and the influenceof deep states, we take account of the use of a fixed low reverse bias in electrochemical C-V profiling compared with an increasing bias in depletion profiling. The interpretation of photovoltage spectra from single layers and heterostructures is described and examples are given of band-gap profiling of laser structures. The article concludes with examples of the characterisation of multiple quantum-well structures including carrier density profiles and photovoltage spectra on structures with periodsless than 200 A.

integrating the etch current and applying Faradays law. Although this method is destructive,the profile can, in Analysis of thecapacitance-voltage (C-V) behaviour of principle, be measuredto unlimited depth.However,the the depletion region of a reverse-biased Schottky barrier requirements the for electrolyte are rather demanding, is a convenient non-destructive method determining for calling for satisfactory barrier and dissolution properties the doping profile in a semiconductor.The chief dison n- andp-typematerial,and, while a number of etches advantage of the method the is maximum for that depth profiling 111-V compounds and alloys have been which can be profiled is limited by electrical breakdown at developed, electrochemical profiling of silicon is still in its high reverse bias, and this can be very restrictive in highly infancy. technique The is now widely used for the doped materials where the depletion depths are small. characterisation of 111-V compounds only not because of Originally this was overcome by alternate chemical the enhanced capability because depth but also the etching and profiling with a temporary mercury barrier, electrolyte barrier can be made quickly without any butthisprocessistimeconsumingand tedious.A bettersampleprocessing,thereby avoiding the risk of modifying solution was proposed by Ambridge and co-workers? - an the sample properties. Furthermore, aversatile instrument electrolyte is used to make barrier to the and remove manufactured by Polaron Equipment Watford, Ltd, UK material electrolytically so bothprocessescan be carried(sometimes called thePost Office plotter or pop - not out in the electrochemical same cell and controlled because of any sparkling performance in drawing the electronically,using automaticequipmenttoperformthenationwidedistribution of sales outlets of postagestamps repetitive etch/measure cycle and generate a profile plot. but rather in recognition of the affiliation of its originators) The depth etch can be measured continuously by is available commercially. As well as providinga convenientbarrierfor C-V i Ambridge and Faktor (1975a, b). measurements, electrolyte the is transparent radiation to
1. Introduction
242/86/010007 0268-1

+ 2 1 $02.50 0 1986 The Institute of Physics

P Blood

at wavelengths shorter about than 1.0pm, thereby facilitating theobservation of avariety of photovoltaic phenomena in GaAs and related alloys. The observation of photovoltageabsorptionspectra in conjunction with etch profiling is particularly useful for the measurement of bandgapand alloy composition in heterostructures for opto-electronic devices. This capability has enhanced the value of the electrolyte- semiconductorcontact in the characterisation of 111-V compounds. The basic principles of electrochemical C-V profiling are documented in number a of original papers by Ambridge and co-workers, butin view of the development of photovoltage spectroscopy and the current widespread use of the instrument for 111-V characterisation it seems worthwhile to review the capabilities, limitations and potential of the electrolyte-semiconductor contact in this area of materials assessment. The review which follows is not a complete surveyof published work in this field, but is a personal assessment based primarily, though not exclusively, on the authors experiences in the characterisation of GaAs/AlGaAs structures. To provide thenecessaryfundamentalbackground, and to put electrochemical profiling in context in the field of C-V measurements a as whole, the first sections develop the basic principles of C-V profiling (0 2) with reference the to limitations imposed by the instrumentation and the sample (0 3). Here we extend the analysis of errors in the measurement of carrier density to include considerations of instrumentaldepthresolution, summarise the influence of deep states and give equations for the effect of series resistance on the measured carrier density. The electrochemical cell has a number of features not encountered in metal-semiconductor contacts such as theHelmholtz-Gouy electrolyte capacitance,the series resistance of the electrolyte and the need to increase the contact area to reduce errors in itsdefinition, all of which haveimplicationsforthemeasurement of C-V characteristics. Furthermore, the electrochemical characteristics of the cell determine the etching behaviour which influences thedepthresolution,control of theareaand overall control of the etch/measure cycle. Published work and some of our own experiences on these topics are brought together in 0 4. In 6 5 we consider the limitations in electrochemical C-V profiling with particular attention to consequences the of the fixed low bias and high electrolyte series resistance encountered in this technique. The principle of photovoltage spectroscopy is outlined in # 6 with examples of applications to heterostructures and composition profiling of laser structures. Quantum-wellstructures now representa significant fraction of the activity on 111-V compounds and in 0 7 we present new results which illustrate theapplications of electrochemical C-V profiling to heterostructures with periods of ~ 2 0 A, and 0 indicate importance the of photovoltageabsorptionspectroscopy in measuringthe characteristic wavelengths of quantum-well structures and checking reproducibility of the well width. The combination of C-V measurement, photovoltage spectroscopy controlled and etching is particularly powerful in the assessment of multiple quantum-well (MQW)
8

structuresforopto-electronic devices suchasquantumwell lasers. In view of their technological importance and the state of theart of their preparation,most of this paper is concerned with layered structures of GaAs/AlGaAs. Quaternary alloys grown on InP are also of importance and the are subject of electrochemical scrutiny in a number of laboratories:most of the principles outlined here are applicable to this material system although, due to absorption in the electrolyte, photovoltage spectra have to be recorded withillumination throughthesubstrate. The limited extent of the authors experience rather than the need forthis modification is responsible for the infrequent reference to these materials this review. in The personal conclusion of the author is that, due to the added ability to photovoltage record absorption spectra, the electrolyte-semiconductor has contact assumeda significance in thecharacterisation of 111-V compounds the depth beyond enhanced profiling capability which was the original motivation for its development. characterisation These techniques are especially appropriate to material for opto-electronic devices and, recent from experience, they will be of considerable value in the characterisation of quantum-well systems.

2. Capacitance-voltageprofiling
2.1. Diode capacitance

The upper part of figure 1 is the band diagram of a metal Schottky barrier on an n-type semiconductor containing densities N, and N , of donors and traps, the latter having energy level E , and taken to be donor like, though this is not essential to argument. the A depletion region is established by the combined effect of the built-in voltage V , and appliedreverse bias V,, and the electron density distribution n(x) at the edge of the depletion region is as illustrated,producingthecharge distribution p(x), made up of positive charge in the semiconductor an and accumulation of electrons in the metal,indicated in the lower part of the figure. The electrostatic potential @ ( x )at anypoint in the depletionregion is given byPoissons equation d2@/dX2 - P ( x ) / E E ~ , = that is
(1)

which may be integrated by parts to give the total electrostatic potential across the contact:

Since the total net positive semiconductor space charge is of equal magnitude to the total excess electronic charge

Electrochemical C-Vprofiling of Ill-V semiconductors

described by a Boltzmann factor it can be shown that n(x)=Nd eXp[-(xd-X)2/2L~]"2 (6)

with the fall-off of n(x) being characterised by a Debye length

L , = (&&oki"/e2Nd)1/2.

(7)

The depletion capacitance is given by C = A dQ/d V where dQ is the fluctuation charge per unit area arising fromamodulation d V in the voltage. We will so that dV, dV. assume that Vb remains constant The principal contributionto dQ arises from the fluctuation in electroniccharge on the shallow donors in the vicinity of the depletion edge causing a fluctuation in the positive spacecharge e(N,(x)-n(x)). There is another contribution to dQ from the change in occupancy of deep states in the vicinity of x 1 Ahere E, crosses E,. States attheinterface between thebarrierandsemiconductor (at x = O ) mayalsocontributeto d e , but this is only significant in the presence of an insulating interfacial layer and for most common materials contacts can be prepared where this layer is very thin (Rhoderick 1978). If the space-charge profile changes by dp(x) in response to the voltage increment d V then dQ=

.m

dp(x) d x

(8)

Figure 1. Energy band diagram of a Schottky barrier on an n-type semiconductor containingNdshallow donors and NI donor-like deep states per unit volume atenergy level E,. The electron density distributionn ( x )at theedge of the depletion region, of width xd, is shown, and the plot of p ( x ) indicates the space-charge density distribution for uniform material.

' 0

and from equation (3) dV=1

&EO
'

1
0

x dp(x) d x

(9)

so that the small signal capacitance is

C=

accumulated in the metal we have

mOA

. -m

.+m

Jr

dp(x) d x

x dp(x) d x

P ( Y ) dy = 0;

if we assume that the width of the accumulation region is very small (screening distancezfew angstrom) such that the potential drop in the metal can be neglected, then the electrostatic potential across the barrieris

with p(x)= e(N,(x)- n(x)) where and d@/dx=O

for

x ~ x , .For uniformly doped material and an abrupt cutoff of n(x) at Xd, p(x)=eN, and the reverse bias band is bending, V = - @,
V = V , + v b = eNdXi/2&&o. (4)

Furthermore, if xd is well defined, integration of the electric field from xd toward the contactgives I//(x)="eNd(xd-x)2/2&&0
(5)

In the absence of deep statesit is possible to derive a result for C as a function of V for uniformly doped material with n ( x ) given by equation (6) (see Sze 1981, p 366: neglecting minority carriers gives the resultfor a Schottky barrier) but for non-uniform distributions of N(x) it is necessary to make three simplifying assumptions, known collectively as the depletion approximation, to obtain an analytic result. It is assumed that the semiconductor can be divided into two distinct regions - (i) space-charge a region immediately below the barrier which is entirely depleted of free carriers and (ii) an interior region which is everywhere neutral - and that (iii) the boundary betweenthese two regions is abrupt. In short, it is assumed that L , g xd so that xd defines precisely the depeletion layer edge; this is equivalent to V $ kT/e. It follows that if we also take the change in deep state occupancy at x, to be abrupt, then equations (8) and (9) become
d Q = u(e,)e&,(x,) d x ,
&EO

+ eN,(x,) dxd
f

(1 1)

and since -e@(x) = E,(x) - E,(&) the conduction-band energy increases parabolically with distance the into depletion region. Near xd this analysis neglects the effect of the electrons, but if we take equation ( 5 ) to be a good first approximation to the form of E,(x) then with n(E)

d V = U(e,)eXINt(X,) dxl

eXdNd(Xd)dXd

(12)

where dx, and d x , are increments the in xd andx1 resulting from the voltage increment and dV, u(e,) describes the responseof the trap to the voltage increment. The first term in equation (1 1) arisesbecausethedeep
9

P Blood

states in the vicinity of x1 emit their trapped electrons to the conduction band at a rate e, where they are removed by the field, and since d V is usually anoscillatory test signal this contribution will only be present when the angular frequency o of the testsignal is less than e, so that the traps can respond. Thus write we

u(en)= 1 u(en)= 0

when o e, when o > e,.

(13)
I
l wze,"
I

If we first consider the case where the contribution of the deep states is negligible ( N , N , ) then equations ( 1 1) and ( 12) in equation ( I O ) give

Frequency,w

c = EEOA/.Yd

(14)

I\

lb)

so within the depletion approximation C is determined solely by irrespective of the space-charge distribution and thevalue of N , at .yd. This result is used in C-V profiling instruments to determine thedepletion depth. When deep states are present. we note from equation ( 5 ) that .yd-.yl is given by

for a uniformly doped material, and L is independent of xd. In fact, for small increments 2 will also remain constant in non-uniform material, although 2 will vary as the DC bias is increased. Thussince d x , = dxd equation(10) gives

Figure 2. Frequency dependence of the measured diode capacitance due to( a )deep states in the upper half of the band gap with emission rate e, and ( b )resistance R, in series with the depletion Capacitance.

The effect of deep states is therefore twofold. Firstly. C is frequency dependentthroughtheparameter u(e,) such that at high frequencies, o 9 e, where u(e,) = 0, equation ( 1 6) becomes

c, = &&OA/Xd,

(17)

may incorporatesome series resistance R , and parallel leakage characterised by a conductance RF'. Capacitance is measured in meters and bridges as the out-of-phase component of the current which flows as a result of an AC voltage of constantamplitude. In the absence of series resistancethis procedure gives C independent of parallel conductance. but when R , is not negligible the measured capacitance is given by the imaginary part of the complex admittance as (Goodman 1963, Bleaney and Bleaney 1976)
C,/C=

identical to equation (14) becausetraps the cannot respond, and at low frequencies, o ~ e where u(e,)= l , , the capacitance increases by AC to a value C, where

{[1 + (R,/RJ]* + (wIR,C)*I"

(19)

with C,= C, + A C as illustrated in figure 2(a). Unlike c,, c, dependsuponboth N,/Nd and xl/xd andhas amaximum value in a given sample when xl/xd-0, i.e. xd-2, of AC= C , N , / N , . The second feature to note, therefore, is that states deep contributedepth a dependence to C, in addition the to dependence inherent in the depletion capacitance because A C varies with .\'d. When .yd is not much greater than i c cannot be , interpreted in terms of S,using equation (14). In materials of only modest qualitythedeepstateconcentration is sufficiently small that theseeffects are negligible, though this may not be so in implanted or irradiated samples. I t is usually possible to determine x d from the depletion capacitance using equation (14) but measurement of C is not necessarily straightforward because the test diode may not be an ideal capacitor but
10

\vhere w I is the angular frequency of the test signal. When R , f 0 C, < C due to both series resistance and parallel conductance, and C, becomes frequency dependent such that C, decreases with increasing frequency as shown in figure 2(b). C, is frequency independent when R , is such that

w,R,C

1 + (R,/R,)

although C, only takes the true value when additionally R J R , < I . Even when R , is large the parallel conductance is sufficiently small in all useful samplesthat R,/R, 1 e and equation ( 19) becomes C,/C=( 1 + W:R;C')-'. Forthe decrease in C, to be less than 19'0 R,<R,,= 0. l(27rfiC)-1 and so errors in C are most likely to occur in highly doped material where C is large. The critical value of R,. RSc,is plotted in figure 3 for a total band bending of 1 V in adiodeonmaterial with N , = I O l 9 cm-3asa function of frequency fifor diodes of various diameters. Evaporated metallic contacts are usually 1 mm in

Electrochemical C-V profiling of Ill-V semiconductors

so that the measurement of C and AC/A V as functions of V gives N ( q ) as a function x& of We will not describe here the various methods which have been developed for measurement the of doping profiles based on these equations (see Blood and Orton 1978):themethodscommonlyemployedare similar in thatequation(22) is utilised by modulatingthe voltage at frequency some o2 and measuring the resulting modulation in C. Alternatively C can be measuredas a function of V and N(Xd) calculated by numerical differentiation. All these methods are subject in varying degree to a number of limitations which can be conveniently divided into three classes: (i) fundamental limitations; (ii) limitations in the instrument; (iii) limitations due to non-ideal characteristics of the sample.

3. Limitations in depletion profiling

3.1. Fundamental limitations Therearetwo limitations of afundamentalnature:the maximum depth which can be profiled and depth the resolution. The maximum depth is limited by the onset of electrical breakdown at high reverse bias in the high-field region of the semiconductor immediately beneath the contact.InGaAsthemaximum field is about4 x lo5 V cm" which correspondstoabout2 x 10l2 charges cm-2 in the depletion region (Sze 1981). In material with N, cm-3 the maximum depth is z 2 O p m whereas for N , z 10l8cm-3 therange is seriouslyrestricted to ~ 0 . 0 pm. Furthermore, since it is not always possible to 2 fabricate ideal diodes with the maximum possible breakdown voltage this limitation can be more restrictive in practice than the theoreticalvalues quoted here. In the depletion approximation xd is well defined and so the depth resolution should be limited only by the depth increment Ax, in the measurement of AC/AV. In reality the depletion depth deduced from the parallel-plate result is given by a combination of equations (10) and(14),

Figure 3. Critical values of the series resistance R,, for a 1% error in C and N, plotted as a function of frequency for , diodes of various areas on material withNd= 10'' cm-3 and a total reverse band bending of 1 V (C/A= 1 O6 pF cm-').

diameter or less, and the figure shows that a capacitance measurement a on 0.25 mm diameter on diode this material using a meter operating at 1 MHz will not be in serious error if R , < 30 R, which is easily achieved.
2.2. Principle of C-V profiling

In the depletion approximation x d is well defined and. provided there is no influence of deep states and that the test diode is a good approximation to an ideal capacitor. .\'d can be determined by measuring the diode capacitance (equation (14)). With these assumptions the depletion depth increases by Axd when the bias is increased by A V and from equation (9)

A V = exdN(Xd)AXd/&&O
and the charge increment (equation is (8))

(20)

AQ = eN(Xd)AXd.
It follows that since

(2 1)

using equations (14) and (20)

AC/A V=-C3/es&,AZN(xd)
or

N(xd)=--

C3 AC -l e&&,A2( A V )

which represents the mean depth of the differential charge distribution in the measurement of C (Kroemer and Chien 198 1). Since p(x)=e(N,(x)- n(x)), in the limit of d V being very small the extent of dp(x) is determined by the Debye length andequation(6)showsthat n(x) falls to 0.05Nd in a distance z 3 L D so the limits of the integral in equation are (23) zxd f 2LD and this represents the fundamental limit the to depth resolution. Further difficulties arise at steps in the impurity profile because the free carriers diffuse down the concentration gradient over a distance of a few L,, establishing a charge dipole within the undepleted material (Kennedy and O'Brien 1969), and as the depletion layer of the surface contact approaches this dipole there is a redistribution of charge both at the
11

P Blood

depletion edge and Panousis 197 1).

within the dipole (Johnson and

3.2. Instrumental limitations

The profiling instrumentdeterminestheaccuracy with which N(xd)and xd are measured and may also determine the depth resolution; ideally, the depth resolution should be limited by the Debye length rather than the instrument. Table 1 gives the contributions of a 30 precision of 1% in the measurement of diameter, capacitance and voltage to the precision in N and x (following Amron 1967).

*
z
c_
D

Table 1. Precision in the derived values of N and x,, due to

1% 30 precision measured in the quantities diameter, fractional and capacitance The voltage. capacitance increment isP=O.l (after Amron 1967).
Contribution to total precision (%) Total Diameter precision in 3a N 3ainx,

IO0 :

C
13.5 0.7

(%)
14 2.1

10-2

I IO

100

4 2

0.02

tapacltance step, p - A C I C

Althoughthediodediametercanonly be determinedto %lo%, in practice this uncertainty affects theabsolute accuracy rather than the noise in any particular profile plot. The overridinginfluence on the precision of N is therefore the precision of themeasurement of AC, and although there is consequently a temptation to make A C largethis introduceserrors in thedetermination of the local value of AC/A V because the C-V curve is not linear and also degrades the depth resolution by increasing the modulation of xd. It is therefore necessary to achieve a balance between these conflicting requirements. The result of Amron(1967)forthe precision in N, denoted 30,, can be simplified when the fractional capacitance stepp = AC/C is small to give
30,

Figure 4. The 3a precision in N ( x )as a function of the fractional capacitance stepP=AC/C for various values the of precision in the measurement of denoted by c. Also C, shown is the error in the evaluation A C l A V d u e t o t h e of non-linearity of theC-V characteristic estimated for uniformly doped material.

controlling A C in some The way. resulting depth modulation is given by equation (20) which, together with equation (25) in equation (24), gives
30,=

&ecXjN(xd)/&&o[A ] . V

(26)

= @c/p

P(0.1

(24)

where c is the precision in the measurement of C. In figure 4 we have plotted 30, as a function of p for various values of c, together with theerror in AC/AV estimated by Amron (1967) foruniformly doped material. This figure shows it is desirable to keep p < 0.1 so that the derivative error is less than the precision due to measurement of C. However, from the result for high-frequency capacitance (equation ( 14))

Thisshowsthattheuncertainty in N increasesas x; producing noisy plots at large depth as noted Baxandall by et a1 (197 l), and also increases proportional to N itself. From equation the (20) instrumental depth resolution decreases with increasing N but is also inversely proportional to x and may be poor at shallow depths. It d can be shown from equations (7) and (20) that AX, < 3LD when x exceeds the critical value d

X,= f [A V](EEO/N~T).

(27)

p = AC/C = - h X d / X d

(25)

The performance of this kind of profiler is not optimum because instrumental the resolution at large depths is unnecessarily small, resulting in a poor precision in N. Profiling with a fixed increment in the electric field A& (Miller 1972) gives a more favourable compromise with a depthmodulationproportionalto N andindependent of xd:
A X d = &Eo[A&]/eN(Xd)

and so if p is fixed the depth step Axd will increase in proportion to xd. For example, in sample a with N-1015cm-3depletedtoz10,umAxdzl,umfor~=0.1 whereasL.zO.12,um. In analogue profiling instruments it is common practice to use a modulation voltage of fixed amplitude [AV] rather the complex than more procedure of
12

(28)

and a precision in N proportional to N and xd:

30, = \/ZeCXdN(Xd)/&&,[ A&

1.

(29)

With complete freedom in spacing the data points it is possible to achieve the optimum depth resolution by

Electrochemical C-Vprofiling of Ill-V semiconductors

controlling A x , for each step so that A x d z L D where L D is evaluated using theprevious value of N . Substituting equation (7) for A x d in equations (24) and ( 2 5 ) gives 30,
=

equation (22) we can write

Nil,, =-- ~ 2 ~ [- ] o~ec m AVrn 0 2

(32)

(30) where C, is the measured high-frequency capacitance given by equation (19) and V , is the voltage across the complete test diode for a voltage V , across the depletion region; w 2 is the (angular) modulation frequency. It follows from equation (32) that

and so the for penalty optimum resolution depth throughout the profile is precision a in N which deteriorates asxd and From this analysis it can be seen that it is difficult to achieve a satisfactorybalance between optimumdepth resolution and accuracy in the measurement of N in depletion profiling and this arises the from coupling between A x , , N ( x d ) and depth according to equation (20).

3.3. Limitations due to the sample

Distortions may be introduced in a C-V profile by deep states in the material and by series resistance and leakage in the test diode. Even when C is measured at high frequency such that equation (17) applies, the may bias be stepped or modulated at a frequency where the states deep can respond leading to a contribution to the indicated value of N. From an equation of the same form as (12) for the modulation depth A x d in terms of the modulation voltage A V an expression for A V / A C can be determined and it can be shown that the measured density (equation (22)) is (see, e.g., Kimerling 1974)

where the derivative in square brackets is evaluatedfor changes of V in phase with V,. It can be shown from a consideration of the complex impedanceof the circuit that

and since w 2z ,&,W, the measurement of C imposes the most restrictive conditions on R , so we can assume w 2 R s C <1 for values of R , and C such that wlR,C< 10 and consequently (34)

where umOd(en)defined as equation (1 3) with w 2 as the is modulationfrequencyand N + ( x d ) is thetotal positive space-charge the density at depletion layer edge: N+(xd)= Nd(xd) when Nt is a deep donor and N + ( x , ) = Nd(Xd)- N t ( x d ) when Nt is a deep acceptor. In material where N + is uniform, or when A x d is small, A x l = A x d . At modulation frequencies the can wheretraps respond, as xd is increased from xd A. to xd $A. profiling uniform material,themeasured density increases by Nt duetothermal emission in the vicinity of x 1 where EF crosses E,. For localised deep and donor acceptor distributions this emission process produces a peak in Nmeas(xd) displaced a distance 1 from the true location of the traps. Additionally the sample with deep acceptors will have a dip in the profile corresponding to the 'compensation' profile N ( x d )= Nd(Xd) - N t ( x d ) (Kimerling 1974). These features are often apparent on profiles of ionbombarded material (Schultz 1974). The contribution of deep states the to profile is determined by the emission rateatthetemperature of measurement, the modulation frequency and the relative magnitude of x 1 and xd in equation (31). In the case of sequential point-by-point measurements the profile measured at low temperatures where e,, is small will also dependuponthe direction in which thebias is changed (Blood 198 1). The measured value of N is also modifiedbyseries resistanceandleakagecurrents in thetest diode. From
+

In effect thecapacitiveimpedance is large at o2 so the fraction of the appliedvoltage V , appearingacrossthe capacitor itself is determined by the resistive components in the circuit. It then follows from equations (19) and (34) that (33) gives (J P Stagg, private communication)

It follows from assumption our above that N,,,, depends on w 1 but not w 2 ,and following our discussion of the measurement of C if we again assumeR,/R I G 1 then

Nrneas/N= [ 1 - ( w I R ~ C ) ~ I - '

(36)

so that N,,,, increases as R , or C increase, and may even change sign. For Nmea,/N<1.01 it is necessary that w,R ,C < 0.3, and the corresponding critical value R,, = 0.3/2nflC is also plotted in figure 3 as a function of frequency for heavily doped material. Again it is apparent that measurement the of C itself imposes most the stringent condition and diodes for which R , is low enough to measure C correctly will give valid data for N . The error in N will be largestat low biasand in highly doped material where C is large. In fact, with diodes where R , is significant wlR,C will decrease as the bias increases and N,,,, will appear to decrease with increasing xd and may indicate the true value at high bias. The series resistance will also increase the perceived value of xd (equation (1 9)) and as C decreases with bias it is possible that the decrease in w,R,C dominates over the V )dependence and there C( is a net increase in C with increasing bias so that the profile plot appears to move backwards (Wiley and Miller 1975).
13

P Blood

3.4. Summary
Depletion C-V profiling is convenient, quick andnondestructive.Using evaporated metal contacts the area is well defined even for diameters ~ 0 . 2 5 which make C mm sufficiently small that there are no series resistance effects even in highly dopedmaterial. In anycase it is often possible topreparetestdiodes withseries resistance of only a few ohms. The combination of small R , and small area (i.e., small C) permits high measurement frequencies to be used (typically x1 MHz) which reduce the influence of deep onmeasurement. states the The principal disadvantage of depletion profiling is the limitation to the accessible depth which is set byelectrical breakdown at high bias: this is very restrictive in highly doped material. Most profiling instrumentsare not ideal in achieving a balance between depthresolutionanduncertainty in N , and this can lead to considerable scatter at large depletion depths.

II l

Figure 5. Schematic diagram of the electrochemical cell used in the profiler, showing the Pt, saturated calomel (SCE) and carbon electrodes, and the pump used to agitate the electrolyte and disperse bubbles on the semiconductor surface.

4. Electrochemical C-V profiling

Therestriction on themaximum accessible depth is the principal limitation of conventional C-V profiling, and to overcome this it was common practice alternately to etch the sample chemically make and profile plots using a temporary mercury Schottky contact(see, e.g., Wood et a1 1979). ThiswasatediousprocessandAmbridgeand Faktor (1975a, b) developed the use of an electrolyte to make Schottky the barrier to andremove controlled amounts of material by electrochemical etching. Since the sample remains in the same cell for both operations the repetitive processcan be controlledautomaticallyand, using Faradays law to determine the etch depth from the integrated etch current, a profile can be plotteddirectly. The principal advantage of the method is that profile depths are not restricted by electrical breakdown and we alsoshowthatthemethod achieves amoresatisfactory balance between depletion depth, resolution and accuracy in N . The disadvantages are that the methodis destructive, it is difficult to measure control area and the of the electrolyte contact with high precision and reproducibility, and depth the resolution is limited by etching nonuniformity. In Q 6 we review theadditionaladvantages which derive fromthecapabilitytomakephotovoltage measurements through the transparentliquid contact. Detailed investigations of the dissolution and C-V characteristics of electrolyte-GaAscontactshave been reported by Ambridge et a1 (1973)andAmbridgeand Faktor (1974), and an extensive review of this and later related work has been given by Faktor et a1 (1 980).
4.1. Operating principles

The key component is theelectrochemical cell, shown diagrammatically in figure 5.The semiconductorslice is held against a sealing ring, which defines the contact area, by means of spring-loadedbackcontacts.Theetchingand measuring conditions controlled are by the potential
14

acrossthe cell and this is established by passing a DC current between the semiconductor the andcarbon electrode to maintain the required overpotential measured potentiometrically with reference to the saturated calomel electrode (SCE). This procedure ensures that the reference half-cell carries no current and is not polarised. The AC signals are measured with respect to a Pt electrode located near semiconductor the surfacereduce to the series resistance due to the electrolyte. A front contact system is available to make the ohmic contact to epitaxial layers on insulating substrates. It has been commonpracticetorepresentthe I-V characteristics of the cell either as plots of V as a function of log I or I as a function of the anodic potential, so in figure 6 we have redrawn the characteristics in the more familiar form of a plot of I ( V ) with forward current in the upper RH quadrant for an n-type semiconductor. The voltage is that of thesemiconductorbackcontact with respect to the SCE so a positive anodic potential corresponds to a reverse bias across the depletion region. The voltage for zero current (dark rest potential) is displaced from the origin in this diagram to due the electrochemicalpotentialsassociated with the reference electrode and the semiconductor half-cell. A Schottky plot of C-* as function a of V for uniform material is illustrated in the lower part of figure 6: the intercept relative to the rest potential represents the built-in voltage Vb of the electrolyte-semiconductor barrier while the doping level is given by the slope of this curve (an equivalent proceduretoequation (22)) at positivegoing potentials with respect to rest the potential, provided significant reverse current is not drawn. When contact the is illuminated with photons of energy greater than the band gap of the semiconductor the reverse current is increased as indicated in figure 6 due to a flow of holes or electrons from the semiconductor into the electrolyte in n- orp-type material,respectively. As illustrated, this causes a change in the rest potential which isof oppositesensefor n- and p-type material and can therefore be used to indicate the material type.

Electrochemical C-V profiling of Ill-V semiconductors

Current

I
Voltage toSCE
I

integrating the etch currentI :

x, = -I I d t
.

M zFDA

(37)

Dark Jlncreasing illumination

Iv
I 1

I I

Safedissolution (light1

l Rest potential (dark1

l I

Rest potential

c-zt

Zero b m

where M and D are the molecular weight and density of thesemiconductor, F is the Faraday constant, A is the dissolution area and z is the charge transferred per molecule dissolved. For GaAs z = 6. A simplified block diagram of the measurement system is shown in figure 7. The etching and measuring conditions are determined by the cell potential and illumination intensity according the to material and type, the alternating etch-measure sequence is controlled automatically. current The etch is integrated and processed to give theetchdepth, which is added to the depletion depthto give thetotaldepth of the depletion edge fromthe original surface.The depletion depth is obtainedfromequation(14) by measurement of C at 3 kHz ( ~ 0 . 1 4 peak-to-peak)and N is derived from V equation (22), measuring AC/A V by modulation at 30 Hz ( ~ 0 . 2 8 peak-to-peak)ata low fixed reverse bias.An V example of a profile of n-type GaAs is shown in figure 8: only the first micrometre at most of this sample could be profiled conventionally before breakdown.

0 Voltage with respect toS C E

Cathodic

voltages

C,ACIAV

Cell Sequence
- t t -

L
Adder

Figure 6 . Conventional /-V characteristics of an electrolyte-n-type semiconductor contact, with V measured with respect to the SCE.The rest potentials in thedark and light are indicated, and the region for safe dissolution where I is independent of Vand proportional to the intensity of illumination is shown. The lower part of the figure is aC- against Vplot measured for NaOH on IO GaAs.

Figure 7 . Block diagram of the electrochemical profiler.

Material is dissolved when an anodic current is drawn by a flow of holes fromtheGaAs,whereasacathodic current causes deposition of material from the electrolyte onto the semiconductor surface. With p-type material the holes requiredforthe dissolution reactionareobtained from the valence band simply by applying anodic an potential which drives the barrier forward into bias, whereas to etch n-type material theholes are generated by illumination under reverse bias. Smooth removal of n-type material is achieved when the anodic current depends upon the illumination intensity but not upon the potential, as illustrated in figure 6. For a reverse bias C(V) measurement on p-type material the potential is switched from an anodic (dissolution) to a cathodic value, and to avoid contamination of the sample surfaceby the cathodic reaction promoted by electrons from the conduction band it is important that the cathodic potential is such that the reverse current during the measurement very small. is Faradays law of electrolysis is used to calculate the depthetched, x,, fromthetotalchargetransferred by

The electrochemical C-V technique has been applied to a wide variety of 111-V compounds and some results have been reportedfor profiling Si (Sharpe et a1 1979, Sharpe and Lilley 1980). The key to successful

Large 0-ring Tiron (MBV 1331

106
c

2
Depth l!.tml

Figure 8 . Electrochemical C-V profile of a doped GaAs epitaxial layer recorded using the 3 m m sealing ring and Tiron electrolyte.

15

P Blood

electrochemical profiling is the characteristic of the contact itself, and in particularthe ability to define the contact area and to control the etching process by bias and illumination with a suitably small dark current under measurement conditions. Given that a suitable electrolyte exists, there are further aspects of the contact, peculiar to the electrolyte-semiconductor system, which must be considered. Firstly the C( V ) characteristics of the system must be dominated by the depletion capacitance of the semiconductor,arequirement which raisesfundamental questions about the charge distribution at the contact as well asconsiderations of the electrolyte resistance,and secondly the arearemain contact must constant throughouttheetchingprocesswithoutundercutting or significant roughening and without seepage of electrolyte under the sealing ring. We review these equations in the following sections.

Table 2. Values of electrolyte resistance measured for 0.1 M Tironandestimatedmaximumvaluesof N for an series resistance (J P Stagg 1982, error <20% dueto unpublished).
Sealing ring

3 mm
R E Nm m

1 mm

650 R 3.5 x IO'^ cm-3

2300 R

10 cm-3

4.2. Contact capacitance

As with the metal-n-type semiconductor contact, illustrated in figure 1, there is an accumulation of negative charge in the electrolyte due to ions which is distributed over a distance of several ionic radii (x 10 A)rather than a few angstroms as for electrons in a metal. The existence of this layer of charge was recognised by Helmholtz and the theory was refined by Gouy and Chapman (see Faktor et ai 1980). We cannot necessarilyneglect the electrostatic potential in the electrolyte as we did in the derivation of equation (3) for the metal contact, and strictly we should consider the contact as the Helmholtz-Gouy capacitance in series with the depletion capacitance. Electrochemical C-V profiling isdoneat fixed low reversebias, so takingatotalband bending of 1 V the largestdepletion capacitanceencountered will be about 1 pF cm-2 (r?zO I 9 cm-3). A simple parallel-plate l calculation of the Helmholtz capacitance for a spacing of one ionic radius (-6 k) gives 1 0 p F cm-2 (e= 7 at high fields) and more detailed calculations which take account of the decay of the ion concentration with distance from the interface suggest larger values (Faktor er a1 1980). A value of x 4 0 p F cm-2 has been measured at 10 kHz by Stagg (1982, unpublished) for 1 M NaOH with a Pt electrode. It would seem that we are justified in neglecting the Helmholtz-Gouy capacitance in all but most the highly doped samples, a practice which is further justified by the observation of linear plots of C P 2 as a function of V for this contact system, characteristic of depletion capacitance alone. In fact, a fixed series capacitance will modify xd but not N as derived from AClA V. The against V plot in figure 6 is for NaOH on GaAs ( 1 7 z lo1 and indicates a built-in voltage V,>, 1.0 V. This increases with increasing pH of the electrolyte (Redstall et a / 1978), but our from own measurements does not depend strongly on doping level. These barriers are significantly higher than metal barriers on n-GaAs ( V,=0.8 V). We find corresponding low V , z 0.4 V in p-type material. and find similar values for in both n-type GaAs and Alo,,Ga0,,As. To minimise the effect of poor definition of the contact

area. large sealing ring diameters of 1 mm or 3 mm (area 0.07 1 cm2) areused for electrochemical profiling; however theresulting increase in C reducesthe criticalvaluefor series resistance errors in C, to R,, z 0 . 2 Q for measurement at 1 MHz on n= 1019 material with the larger ring, as shown in figure 3. This is very restrictive because the electrolyte resistance in the standard cell can be large(wehave measured 650 Q for 0.1 M Tiron with 3 mm ring, table 2 ) , so toease thislimitation a lower measuring frequency must be used: 3 kHz is used in the standard instrument which, according to figure 3. means that R , will influence measurements when n > 1019 and R , 2 lo2 Cl.
4.3. Contact area

Ambridge er ai (1980) have identified three components to the contact area, illustrated in figure 9. The central illuminated area A , is the region which is etched in n-type material. while the total wetted area within the sealing ring A = A c + A is the area etched and measured in p-type material. The instrument the corrects capacitance measured on n-type material for capacitance of the unetched annular contact of area A , . There is a further outer excess area A , due to seepage of electrolyte under the sealingring which is particularlytroublesome when measuring hi-lo profiles, andhas been modelled asa frequency-dependent capacitance whose contribution can be reduced by choice of alow-conductivityelectrolyte (Ambridge et a/ 1980). The areas A , and A , can be measured and controlled with reasonable accuracy but A , is very variable and depends to some extent on the viscous properties of the electrolyte. Ambridge et a / (1 980) report

Wetted area
AqZACtAE

c,
16

Figure Diagrammatic cross Section of the between the sealing ring and the semiconductor sample, showing the outer excess area due to leakage of electrolyte.

Electrochemical C-Vprofiling of Ill-V semiconductors

thatTiron is particularlysatisfactory inminimising the effects of the area outer A , , and gives a short-term reproducibility in thearea A , of ~ 2 % Nevertheless,to . minimise the fractional uncertainty in the area sealing rings of 1 mm or 3 mm diameter are used -larger than the metallic contacts used in depletion profiling. Thesepointsareapparent in thedata of figure 10, which shows measured values of N using Tiron, HCI and NaOH electrolytes with the small sealing ring ( 1 mm) plotted as a function of f i T , the average value measured with Tiron. Tiron and HC1 give similar results, but NaOH gives highervalues of N which we attributeto seepage under the ring. The dependence of N / N , upon R is , similar to that predicted by the excess capacitance model of Ambridge et a1 (1980) (see their figure 4), and means thatthe excess areacannot be compensated simply by using a different value for the area.

preferred electrolyte for GaAs(Ambridge et ai 19801, although the higher electrolyte resistance imposes a lower limit on the maximum value of C which can be measured without R , errors, and hence limits the maximum value of ,V which can be accurately profiled. Ammonium tartrate solution has been suggested for profiling GaAs, AIGaAs, GaP and GaAsP, although the area definition is poor: we have etched some n-type samples of GaInP with this solution but there were serious non-uniformities on p-type material. We have also used NaOH for profiling AIGaAs, althoughagaintherecan be problems defining thearea accurately. HCI is recommended for InP-based materials and we have used it occasionally on GaAs.

5. Limitations of electrochemical C-W profiling

5.1. Depth resolution and accuracy

*r

0
1015
106
1017

108

1019

A, (crn-~

Figure 10. Values of N measured with various electrolytes on different samples of GaAs using the 1 m m diameter sealing ring plotted withrespect to thevalue obtained with Tiron (A,) (J P Stagg 1982, unpublished). 0, 1 M NaOH; x 0.5 M HCI; 0,0.1 MTiron ( / V T ) .
I t is alsoimportantthatthearearemainsconstant during etching the process so that the profile is not distorted. Principally this meansthatthecratershould remainsmooth - this is alsoanimportantcondition in maintaininggooddepthresolution.Gooduniformity of etching n-type material is achieved using short-wavelength illumination (-550 nm) which is strongly absorbed at the surface producing a photocurrent which is largely independent of the depletion width and diffusion length, both of which could vary across the crater. Dissolution by drawing a dark current in reverse bias must also beavoided because this leadsto severepitting andanincrease in the contact area (Ambridge and Faktor 1974). A Talysurf trace of theetchedcrater gives a useful indication of grossroughnessand provides a measurement of crater depth which can be compared with theindicateddepth, making due allowance for the depletion depth.

Electrochemical profiling overcomes the fundamental depth limitation in depletion profiling and in principle offers the capability to measure depth. to any The fundamentalDebye length limit tothedepth resolution remains because the smearing of the edge of the spacecharge distribution is determined by the doping level in the vicinity of .yd. The influence of instrumental limitations on the profile is rather differentforelectrochemical profiling compared with depletion methods. Since theetchstep Ax, can be made very small, the limiting depth resolution is due to the roughness of the etched crater dx, and the depletion depth modulation Ax,:

(A-Y,,t)2= (&Ye)*

+ (AX,)2.

(38)

Themeasurement is madeata small fixed appliedbias with constant modulation amplitude [ A V ] , and if we assume the doping density is approximately uniform over the depletion region, then equations (4) and (20) give

and combining this with equation (7) for L gives ,

4.4. Comments on electrolytes

Initial C-V experiments by Ambridge and Faktor (1974, 1975a, b) used KOH electrolyte but, to reduce the effect of the outer excess area, Tiron (Faktor Stephenson and 1978) with a higher resistancewaslateradoptedasthe

At temperature, room and with V, + Vb z 1.0 V, modulation of 0.28 V peak-to-peak gives Ax,, z 1.2LD5so since A s , is less than a few Debye lengths and independent of N the depth resolution for AC/AV is alwaysdetermined by theDebye length ratherthanthe modulation.The overall instrumentaldepth resolution is therefore controlled primarily by the influence of the etching process on the flatness of the crater. Our observations suggest that the amplitudes of depth undulations in the crater are proportional to the mean etch depth and amount to~5-10%of the depth etched. The precision of the differential capacitance measurement of N can be estimated (assuming N to be uniform over S,) by substituting equation (4) into equation
17

P Blood

(26) to eliminate ,V:

The uncertainty in N due to imprecise measurement of C is independent of N and the depletion depth. However, in the case of electrochemical profiling there is the possibility of furtheruncertainty in the value of N within a given profile due to craterroughness,contributionsfromthe sides of the crater and gradual seepage electrolyte under of the sealing ring, although these are difficult to quantify.

\ 1 f.30

HZ

5.2. Influence of deep states

The sensitivity to deep states differs from that of depletion profiling because the measurement frequencies are lower and because the depletion depth remains small, and constant in uniform material, so that the term XI/&, = 1 @.yd can be much less than unity (equation (3 l)). In fact, these two effects are linked through the energy level of the trap which determines both e, and A. Considering first the influence of /I, when u(e,)= 1 equation (18) gives the capacitance as
l.0L

..

l.lr
- 1v

1.0

where C, is independent of N, (equation (17)). and equation (3 I ) gives

(43)
where we have taken the simple example of a donor-like trap. For this example we assume the material is uniform, so that equations (4) and (15) give

(44)
and we assume E , is sufficiently close to the conduction band that it is reasonable to make the approximationE , E , 2 E, - E,. Figure I 1 shows xl/.Yd. co/c, and Nmeas/Nd as functions of E , - E , calculatedfromequations (44), (42) and (43) for V = V, + V, = 1 V and 10 V and with the specific value of N , = 0.1Nd.Since the perturbations of the measuredquantitiesscaleapproximatelyas N,/Nd these plotsindicate the relative magnitudes of the effects in a given sample. We have calculated the emission rate of the trap at 300 K for the specific example of a capture cross section of IO-I5 cm2 using the detailed balance equation (Blood and Harris 1984; equation (6)) and this is given in the upper part of figure 1 I . With the small fixed bias used in the profiler x1/Xd becomes small as E , - E , increases, causing an increase in C, away from its true value anddecrease a in N,,,, towards the true value. Thecapacitance is measuredat f, 3 kHz so that only traps with E,-E, < 0 . 3 5 eVwill = respond and the maximum error in C, (and XY) be will z 6% for N,/Nd= 0.1. N,,,, is obtained by modulation at f2 = 30 Hz and will therefore deviate from Nd by at least 3% up to the maximum possible error of 10% ( = N,/N,),
18

Figure 11. Calculations of the influence of deep states on the measurement of C and N as a function of trap energy NI level E, - , E t . In these examples we have taken =0.1 Nd and have assumed thatE, - E F is negligibly small. The upper plot indicates the relation betweene, and E, -E, for an cm. electron capture cross section of I 0-15

due to traps shallower than ~ 0 . 4 eV. Since V , remains 8 fixed and .ul/.ud is independent of Nd these perturbations will remain constant throughout an etch profile for a given trap energy level and concentration. The lines calculated for V = 10 V indicate the changes which occur in .Yl/.Yd and the measured quantities as the bias is increased for a depletion profile. The energy level positions for traps influencing a measurement of C at 1 MHz and N with modulation at 3 kHz are marked on the figure. I n accordance with equations (16) and (3 1) the perturbations in C, and N,,,, decrease increase, and respectively, as V , increases. Taking account of both the different measuring frequencies and the effect of the DC bias, we conlcude from figure 1 1 that in the presence of deepstates depletion profiling will give a more reliable value of x because the , bias is greater and the capacitance is measured at a higher frequency than in electrochemical profiling, restricting the effect to only shallow traps. Electrochemical profiling

Electrochemical C-Vprofiling of Ill-V semiconductors

gives a more accurate value of Nd throughout the profile because V remainssmall,andalthoughthismethod is sensitive to deeper traps because of the lower modulation frequency these have a smaller effect on N,,,, because of their larger l. values.

.yd

5.3. Series resistance

Because of thelargeseriesresistanceoftheelectrolyte (table 2) and the large capacitance due to the contact area. series resistance are concern errors greater of in electrochemical C-V profiling than in depletion profiling. Although the measuring frequencies are relatively low to reduce these errors, large values of C will be encountered because the profiler can be used on highly doped materials where depletion profiling is of little value due to electrical breakdown. The dependence of N on the fourth power of R , (equation (36)) has been verified experimentally (Stagg 1982. unpublished results) by inserting carbon resistors in series with the cell. Figure 12 shows that as predicted [ 1 (.Vmea,/,V)~ varies linearly with R , with a slope consistent with C calculatedforthedoping level andanintercept which gives R , = 2.75 k n due to contact and electrolyte. in agreement with the value in table 2 . In table 2 we give the maximumvaluesof N whichcanbemeasuredwitha series resistance error less than 20% for the values of R , measured for 0.1 M Tiron. These limits can be increased by using a more conductive electrolyte, but contact area errors may then be introduced.

and C therefore remain fixed. resulting in values of N and which are larger than their true values but the indicated profile remains as flat illustrated in figure 13. This contrastswithdepletionprofilingwhere C decreases and so the errors decrease through the plot (Wiley and Miller 1975). The error in the electrochemical plot is more difficult to detect, so it is useful to check that the indicated depletion depth and doping level are consistent (equation (4)). Whenprofilinglayers on semi-insulatingsubstrates R , increasesdepletion approaches as the edge the substrate, which to apparent leadsan increase in N . although this is often preceeded by a decrease due to part of the etch area penetrating through to the substrate as a result of non-uniform etching.
I I Depletion
I proflle

.m _
c

I l \ \ \

J" "

Electrochemical profile

" ; t
Impurity proflle

Figure 13. Distortion of a uniform profile by a large series resistance for depletion and electrochemical - V profiling. C

Errors will also introduced be by a high parallel conductance (G=R;') - which, if actingalone,serves to decrease N,,,, (equation (35)). Furthermore, in highly dopedsamplesthere is only a smallvoltagerangeover which G is acceptably small and this may be less than the voltageswingappliedtomeasure C and AC/A V . While this source error of is not in principle unique the to electrolytebarrier, it is rarelyencountered in depletion profiling because this technique is not usually applied to highly doped samples.

5.4. Summary
Figure 12. Plot [ l of as a the function of resistance RI added in series with the electrochemical cell. The linearity of the plot confirms equation (36) for the effect of resistance, the series andintercept gives R,, the resistanceelectrolyte back of and contact (J P Stagg, unpublished).

Seriesresistance will distorttheprofile in a different way to depletion profiling. For example, with a uniformly doped layer on a conducting substrate R, is due to the electrolyte and contact and remains constant through the profile:likewise,sincethemeasurement is done at fixed reverse bias. C also remains constant. The errorsin both N

I n summary, the electrochemical profiler is not limited by diodebreakdownandasaconsequenceofoperationat fixed bias the accuracy in N is independent of N and depth andthedepthresolutionofthedifferentialcapacitance measurement is always limited by the Debye length rather thantheinstrument.Etchinguniformity is theprincipal instrumental to depth limit the resolution, area and definitionthe accuracy. limits absolute Helmholtz capacitance and electrolyte resistance may limit operation of theinstrument on highlydopedmaterialwhere C is large. the and choice low of operating frequencies to minimise R , effects results in increased sensitivity to deep
19

P Blood

states in the measurement of C and x d , although the low applied bias means that N is not seriously affected.

6. Photovoltage spectroscopy

An advantage of an electrolyte contact is that is it transparent to radiation at wavelengths below z 1.2 p m wherethere is negligible absorption by water.Withthe addition of a variable monochromatic light sourcethe electrochemical cell becomes a powerful tool for the study of the photovoltaic behaviour of materials with E , 2 1 eV.
6.1. Basic principles

for a ( i ) s d < 1 and with the thickness of undepleted material >4L; T is the transmission factor of the contact. The absorption coefficient a z lo4 cm" at photon energies above the absorption edge, and since x d z 1 p m t h e condition a(l).yd < 1 is satisfied for the initial part of the absorption edge at lower photon energies. Furthermore, since L z 1 pm then at the onset absorption of a ( i ) L< I and equation (45) can be written

Jph(2)= eFT(L f X d ) a ( A )

(46)

Thebanddiagram of atransparentcontactonn-type material under illumination with light with hv > E, is shown in figure 14. Photogeneratedelectronsand holes are separated by the electric field such that for n- and ptype material holes and electrons, respectively, are swept to the front contact. The sign of the photocurrent is therefore indicative of the semiconductor type in the vicinity of the contact, and this is manifest in the change in the rest potential which is observed with the broad band source used for etching (see figure 6).

so JP&) is proportional to a(A)and the spectral response of the photocurrent defines the absorption edge, and hence the band gap, of the near-surface material. It is often desirable to measure an open-circuit photovoltage current rather to than a avoid electrochemical etching or deposition at the interface with the sample. In this case photogenerated the carriers separated by the field build up charge on each side of the depletion region causing a reduction in the band bending which in turn causes a forward current to flow through the contact. In the steady state an open circuit voltage V,, is established which sets up a forward current which is equal and opposite the to photocurrent. For a barrier with ideality factor n, a series resistance R , and leakage R , the net current is (following Rhoderick 1978)

Transparenl electrode
_ N v ,

x e x p -(V--ItOtRs) nkT

(47)

so that when I,,, = AJ,,, = 0

and if the photovoltage is small such that V ,

< kT/e then

which, with equation (46), shows that under small signal conditions and a L , a x d < 1, the photovoltage is proportional to both a and the photon flux F :
Figure 14. Band diagram of a transparent contact on an n-type semiconductor indicating the driftand diffusion components to the photocurrent.

For an incident photon flux F at wavelength A, the photocurrent density JP, produced in a semiconductor with diffusion length L , absorption coefficient a(A) and contact depletion width xd is made up of a drift component due to electron-hole pairs separated in the region 0 < S <.vd andcomponent to a due the diffusion of minority carriers beyond s d to the depletionedgewhere they are then swept out by the field (see figure 14). These contributions combine to give (Stagg 1982)

The open-circuit photovoltage is independent of R , but its magnitude is influenced by the leakage currentof the diode as well asthebarrier height (through lo), diffusion the length and depletion depth.
6.2. Applications of photovoltage spectroscopy

We have built system a for measuring photovoltage spectra in GaAs AlGaAs and in conjunction with electrochemical profiling using a light pipe andremotecontrolled prism to introduce chopped monochromatic radiation through the window of the cell without removing it from the instrument. The photovoltage signal is detected between thebackcontactsandthePtelectrode using a

20

Electrochemical C-Vprofiling of Ill-V semiconductors

lock-in amplifier with an input impedance of 100 MR. The cell receptacle is screenedtoreducepick-upand when very high sensitivity is required the electrodes are connected directly to a battery-poweredhigh-impedance pre-amplifier within the screen. Thephotovoltagespectra in figure 15, recorded for samples of GaAs and A10,,,Gao,8,As, showthe shift of absorption edge with alloy composition due to difference in band gap. In direct gap materials a(hv) is proportional to ( ~ v - E , ) ~(Pankove and 1971) in principle an extrapolation of a2(hv)shouldlocate E,. In practicethese plots arenot usually linear, probablybecause of the effect of electric field onband (the the gap Franz-Keldysh effect) and impurity tails in highly doped material. Klug and Neuman (1976) have used a linear extrapolation and we have found that the wavelength of the half-height of the edge gives quite good agreement with luminescence data for AlGaAs at doped =lo cm-3. Despite these reservations, these measurements provide a quick selfconsistent method for checkingalloy composition.

444

g 6 $ g

Figure 16. Photovoltage spectra recorded a t the locations indicated by interrupting an etch profile through a GaAs/AIGaAs DH laser structure. A positive signal corresponds to an n-type surface photovoltage.

Wavelength lnm)

Figure 15. Surface photovoltage spectra from n-GaAs and n-AI,Ga, -,As. Three common methods of identifying the band edge are indicated: the break point gives x z 14.8%, a linear extrapolation gives x % 14.2% and the half-height position gives x z 15.5%.

This technique has been applied to the characterisation of GaAslAlGaAsheterostructures by Wakefield et a1 (1 979): byperiodically interruptingtheelectrochemical profiling process, it is possible to record photovoltage spectra at various etch depths through the structure and hence obtain the local band gap and composition. Figure 16 shows a selection of photovoltagespectra recorded at different depths while performing an etching profile of an AlGaAs/GaAs double heterostructure laser. The initial spectrum (1) indicates a p-type GaAs contact layer and subsequent etchingreveals in sequence (2) the ptype AlGaAs cladding layer, (3) the n-type GaAs active region, (4)the active region and the lower-n-type AlGaAs cladding layer (the contact depletion region includes both

the GaAs and AIGaAs) andfinally (5) the n-type AlGaAs layer alone. Stagg et a1 (1982) have used this procedure to construct composition profiles in conjunction with doping profiles for DH laser structures grown by molecular beam epitaxy.Figure17(a)showsdata for a structure where, due to surface accumulation the Sn n-type dopant during of growth, thep-n junction is displaced from themetallurgical junction which delineates the upper interface of the GaAs active region. Notice also the increasein the n-type doping level atthe loweractiveregion interfacecaused by the reduction in the growth rate when the A1 flux is turned off (the growth rate is proportional to the total flux of groupI11 elements).Similar experimentshaveshownthatthe junction is correctlylocated when the p-doping and ndoping levels are similar (figure 17(b)) or when Si is used todopethen-typelayers.Theinterpretation of these measurements is unambiguous because the determination of composition, type and doping level are made together on the same structurewith a common depth scale. The depth resolution in the vicinity of the active region is often degraded by craterroughnessobscuring useful information. In our experience a slow chemical etch (e.g., 5H2S0, : H 2 0: H 2 0 2 )leaves a relatively smooth surface so we use this to remove most of the upper cladding layer then profile electrochemically across the active region with an expanded depth scale and reduced crater roughness. Although we have concentrated attention on the photovoltage generated at the electrolyte-semiconductor contact - the surface photovoltage - photovoltages may also be setup within thesample wherever electron-hole pairs are generated separated and by band-bending
21

P Blood

1 0 ' ~ ~ Carrier P i concentrati 01

la1

km-7

AI content
( X )

Depth (pm1

Figure 17. Doping profiles and composition profiles for two laser structures DH ( a )with and ( b )without a displaced junction and active region (Stagga/ et 1982).

regions. Figure 18 shows diagram the band and photovoltagespectrumof a singleheterostructure of ptype GaAs and AlGaAs grown on an n+ GaAs substrate. The dominant feature the of spectrum is an at edge s 5 9 0 nm producedthe at surface contact the with AlGaAs ( 2 5 2 % ) but there is also a signal of opposite sign which persists at longer wavelength cuts at and off 880 nm. This is generatedthe at buried GaAs p-n junction by photons of energy less than the band gap of the AlGaAs which are not absorbed in the upper layer of the structure. Since the measurement is made under opencircuitconditions it is onlynecessaryforchargetobe redistributedacrosseachband-bendingregion.unlikea photocurrent experiment where current must flow through the and samplethe external The circuit.observed photovoltage is simply the algebraic sum of the voltages generated throughout the sample at a given wavelength. It is possible that a photovoltage signal is also generated at i 600 nm by the band bending at the heterobarrier and < this will oppose the surface photovoltage signal, but since the light is attenuated in the material at these wavelengths thesurfacesignal will alwaysbedominant.Wedonot anticipate a strong photovoltage signal from the GaAs at thisinterfacebecausethesense of thebandbending is such that the minority carriers generated in the GaAs are
KLB 2 4 6

not swept across the barrier region, although there may be a small effect due to accumulation of holes at the valenceband spike which is of the same sign as the p-n junction signal. I t can be seen that there will be a negligibly small signal gap from material narrow in double a heterostructure even though attenuation of the excitation through the upper cladding layer is small. Spectrum ( 2 ) in figure 16, recorded in the upper cladding layer of the DH laser. gives no indication of the GaAs active region in the structure. though material even this is photoexcited. Notice also that though the GaAs signal (1E 880 nm) in figure 18 is of opposite sense to the surface signal from the p-AIGaAs. it cannot be interpreted simply as an 'n-GaAs' signal as if it were at the surface. The sign of the voltage indicates the sense of the band bending and the positivegoing voltage is due to photogenerated carriers from both n and p sides of the junction. Thetechniquesdescribedareapplicabletomaterials with E , 3 1.2 eV, but in narrower gap materials, suchthe as quaternary alloys used in long-wavelength lasers, there is strong absorption in the aqueous electrolyte in the vicinity of the band edge. In this case photovoltage spectra can be obtained by illumination through the substrate, provided it is transparent (as it is for GaInAsP on InP), to generate a signal at the electrolyte contact.

t
0

I -

700

800

900

a J

f
> +
. c

Wavelength lnml

hclh
"

"-

" "

Electrolyte

PAlGaAs

1,

PGaAs

I,

"GaAs

Figure 18. Photovoltage spectrum from a p-type AIGaAs/GaAs single heterostructure on an n-type GaAs substrate showing the signal from the buried GaAs p-n junction.

22

Electrochemical C-V profiling of Ill-V semiconductors

7. Thin multilayer structures

In this section we describe applications some of the electrochemical profiler to assessment the of multiple quantum-well (MQW) structures, with examples taken from recentwork in ourlaboratory using samplesgrown by molecular beam epitaxy.
7.1. C-V profiling

Figure 19 is anelectrochemical C-V profile througha single n-type AIGaAs-GaAs heterobarrier showing depletion of carriers in the AlGaAs and accumulation in the GaAs due to the form of the conduction-band profile
Narrow gap

W Ide gap

Figure 20. Conduction-band (E,) diagram and plots of the

actual, n ( x ) ,and perceived, ? ( x ) , free-carrier profiles for GaAs ( a ) and a AlGaAs ( b )heterobarrier. Vda and V,, are the diffusion potentials on each side of the barrier (after Whiteaway 1983).

determined, the discontinuity may be calculated by noting from figure 20 that

e$ = A E c + (Eca- EF) - (Ecb- EF).

l
1017

D 94
01

0.2 Depth (pm1

0.3

Figure 19. Electrochemical C-Vprofile through an n-type AIGaAs-GaAs heterobarrier.

acrosstheinterface illustrated in figure 20. Duetothe averaging effect of the Debye tail the measured C-V profile ;(.v) does not correspondtothetruefree-carrier profile /?(S),and n(x) does not correspond to the impurity profile because of carrier diffusion in the region where the bands are bent. Since the band bending at the contact in an electrochemical profile is much greater than kT/e, this measurement should give the same results for i ( x ) as a depletion profile and this is confirmed in the simulations of Whiteaway (1983). A detailed analysis of a profile such as figure 19 requires solution of Poissons equationforthe assumeddoping profile in eachlayerandtheassumed discontinuity AEc (e.g., Whiteaway1983,Missousand Rhoderick 1985). However,KroemerandChien(198 1) have shown that the Debye averaging process conserves both the increment charge and its total moment throughout the profile so the electrostatic potential t,b across the barriercan be calculated using equation (3) with /?(.v) replaced by i ( x )and the origin transferred to the interface so thatequation (2) is satisfied. With @ thus

Experimentstomeasure AEc by this methodhave used data for ri(x) obtained by depletion C-V profiling (e.g., Kroemer et a1 1980),and while in principlethese data could also be taken from an electrochemical C-V profile provided the etch step ( A x , ) and the roughening (dx,) are sufficiently small, the method is very sensitive to the diode area. Unlike a depletion profile where h(x) and x are both obtained capacitance from a measurement and t,b is independent of the measurement of area, in an electrochemical profile where the depth scale is obtained predominantly from the dissolution current the integral in equation (3) dependsupon i ( x ) obtainedfromequation ( 2 2 ) and s d . u z [ x l 2 obtained from equation (37), which combine to give I C / K A - ~ Even if A can be determined to . sufficient accuracy, we emphasise that the substitution of ;(.v) for /?(.v) is valid only for averaging by the Debye tail and will not be valid if the profile is smeared out by etch roughening, so although the discontinuity is evident in a profile such as figure 19 this is probably not the preferred source of data for i ( x )to determine A E c , Figure 21 shows a profile recorded using a 1 mm sealing ring on an MQW structure with 60 GaAs wells separated by A10,,,Gao,,3As barriers doped and p-type throughout with Be: the profile shows 60 spikesspaced 184 8, apart, which we associate with carrier accumulation in the wells, as in figure 19. The striking feature is that the wells are clearly resolved even at a depth of 1.2 p m where our usual roughness criterion suggests A Y , z 1000 A and it seems that the multilayer structure
23

P Blood

t 106

6 0 - p e r ~ o dm

KLB 266
AXe35

I
04

l
0.8

R
l

1.2

Depth (pm1

Figure 21. Electrochemical C-V profile through a 60-period GaAs/AIGaAs MOW structure doped with a constantBe flux. The etch step between data points was Ax, = 3 5 A.

itself is smoothing out the etch. It is also noteworthy that the peak spacingaveragedoverthe first 10 and last 10 wells is 182 A and 186 A,respectively, indicating that the depth scale is accurately maintained throughout theprofile (assuming reproducibility in the period of the structure). Figure 22 is part of a profile recorded on a similar sample at higher depth resolution. The profiles for a set of structures all with 60 GaAs wells and with the same period but doped throughout with different concentrations of Be are shown in figure 23. The two samples with the lowest doping (< 10 cm-3) have flat profiles whereas the othersamplesshowadampedfluctuating signal, due to the wells, but not clearly resolved because of the large etch depth increment during profiling. To interpret the profiles in figure 23 we must consider the valence-band diagram of a multilayer GaAs/AlGaAs structure. shown in figure24. When the layers are thick (say z 1 pm) there is accumulation and depletion of mobile holes in the GaAsandAIGaAs, respectively, on each side of the valence-band discontinuity AE,. Taking A E , z 0 . 2 5 A E g (Dawson et a / 1985), we estimate A E , s O . 1 1 eV for our samples so the thinnest depletion region ( d ) is x 150 A wide in themost highly doped sample ( s 3 x 10 cm-3 in AIGaAs). (We have assumed the band bending in the barriers is zOSAE,.) In a multiple quantum-well structure with barriers only 175 8, wide the barriers are thereforedepleted and all the mobile charge

resides in the wells as depicted in the lower part of the figure. In less highly doped samples d will be even greater andtheband bending over h & , will be less. Moreover, since L , 5 5 5 A,the accumulation regions associated with eachinterfacemergeto give anapproximately uniform accumulation of holes in the well. When the structure is depleted by an external contact the space-charge density is approximately uniform, being determined by the impurity distribution. For N , = 2 x IO we canestimatefrom equation(4)thatfor V + V ~ 0 . V, as used for the , , 4 profile, x x 500 i and the contact depletion extends over d i several wells. We have shown in 9 5 that in principle thedepth resolution of the C-V measurement is limited by the Debye length.butsince thecarriersare confined overa distance L , which in these structures is less than L D (> 80 A ) the resolution will be controlled by the relative magnitudes of the etch step Ax, and depletion modulation A.yd compared with L , and Lb. From equation (20) we have estimated Axd for I/, + Vb = O S V and AV=O.28 V peak-to-peak as used in the instrument for the average doping levels indicated by each of theplots in figure 23. The values given on the figure show that only in the more highly doped samples is A.yd sufficiently small to resolve each period (Z200 A) of the structure, but since A x , E 100 A the carrier accumulation is not well resolved into continuous peaks.In figures

Depth Ipml

Figure 22. Part of an electrochemical C-Vprofile through a 60-period similar to that in figure 2 1 recorded with a small etch step Axe z 10 A.

MOW

structure

24

Electrochemical C-Vprofiling of Ill-V semiconductors

1o'*

E
Axd=1688(

Axd=306J(

10l6

Depth Ipml

Figure 23. Electrochemical C-Vprofiles of a set of similar st structures doped throughout at various concentrations with Be. The etch step was x, z 83 A and the depletionstep, estimated from theaveraged measured doping level, is shown on each plot.

is conserved in theDebyeaveraging of the profile at each interface (Kroemer and Chien 1981), the integrated charge under each peak in figure 22 should be equal to the dopantconcentration per unit area per period. Witha small correction for overlapping peaks the charge peak per is about 5.7 x 10" cm-*, the and charge per period, calculatedfromtheobservedAlGaAsdoping level and period. and with allowance for the higher doping level in the GaAs due to the lower growth rate, is estimated to be 5.5 x IO" cm-2. These are in reasonable agreement: the true doping level in the GaAs may be even higher if there is some preferential incorporation of compensating centres in the AIGaAs. The depletion step could be reduced by reducing A V : for example, if A V=O.lVpeak-to-peak then Axd z 50 A for themost highly dopedsample in figure 23. Although we have madenumber a of simplifying assumptions, the arguments presentedhere account for the general features of our profiles. Charge accumulation in quantum wells can be observed when the doping density is sufficiently high that Axd is less than the well spacing for the voltage step used in the measurement, and when the etch step Ax, is less than the well width. Our observations imply that the roughness of the etch crater dx, is much smaller in these multilayer structures than in homogeneous samples and we interpret the damping of the oscillations in the profile to be caused by an increase in dx, with increasing etch depth (e.g., in figure 23). 7.2. Photovoltage spectroscopy Another aspect of the characterisation of MQW structures using theelectrochemical cell is theobservation of the absorption spectrum of the MQW using photovoltage (PV) spectroscopy. spectrum The in figure 25 for the least doped sample of figure 23 has two groups of two peaks corresponding the to excitonic transitions between electrons and light and heavy holes for the n = 1 and n = 2 confined particle states (Dingle 1975). With correction for the binding energy of the 2D exciton (x9 meV) and the

AlGaAs

AlGaAs

GaAs

l !

Wavelength (nml

Figure 24. Valence-band diagram of an AIGaAsIGaAs multilayer structure where thelayer thicknesses, L, and Lb in wells and barriers, respectively, are greater than and less than the depletion and accumulation distances d. ( a )Thick layers: ( b )quantum well.
n=l

21 and 22 Ax, has been reduced to 35 A and 10 A, respectively, and the peaks then emerge as well defined features. Since contact the depletion depth is greater the than period of thestructureand since thechargeincrement

t
Figure 25. Surface photovoltage spectrum of a p-type MOW structure with 55 A wide GaAs wells (same as the low doped sample of figure 23).

25

P Blood

AlGaAs composition obtained a from surface PV spectrum. it is possible to use these data to derive a value for the well width assumingindependent wells: forthis sample we obtain L , = 55 & 1.5 8,(using the same analysis as Dawson er a1 ( I 985)). We have assumed that thereis no significant shift of the absorption peaks due to the electric field in the depletion region. An important application of this technique is the characterisation of MQW laser structures.Adoptingthe same principle as'band-gap profiling', it is possible to determine the composition of cladding and waveguide regions, and the wavelengths of the absorption peaks of the MQW active region as illustrated in figure 26 (Blood er a1 1985a). It is thenpossible to make direct comparison with the observed emission energies of the same structures processed intolasers(Woodbridge et a1 1984),without recourse estimated to well widths and theoretical calculations of the associated transitionenergies.
A

possible to use the signal from a buried p-n junction, as shown in figure 18,monitor to the light transmitted through an MQW using the structure indicated in figure 27.

GoAs

BC

Figure 2 7 . Schematic diagram of a structure with a GaAs p-n junction behind a Maw sample where it acts as a detector for transmitted light. The associated band diagram is shown in the lower part of the diagram.

Following derivation the of equation (50), the photovoltage from the junctionis (Blood 1985)

550

600

650

700

750

800

Wavelength (nm)

Figure 26. Photovoltage spectra recorded at various stages during electrochemical profiling of a MQW separate confinement heterostructure laser (Blood et a/ 1985a).

where TMQw(A), R(A) and F(A) are transmission the through MQW, junction the the spectral response and incident flux. respectively. The signal from this structure (figure 28) shows a doublet feature nearA = 845 nm due to absorption in the MQW reducing the light intensity incident on the junction, and since F(A) and R(A) are slowly varying functions of A the spectrum below 850 nm follows qualitatively the transmission spectrum TMQw(A). A structure without the MQW gives a similarsignal to that
Sample 157 100-perlod naw structure

It is interesting to speculate on the origin of the photovoltage in these structures. If the photoexcited e-h pairs remain confined in their original wells then the redistribution of charge by the field can only occur within each well so the observed photovoltage is due to dipoles set up across individual wells. However, the electric field may enhance the emission rate of carriers from the well, probably by tunnelling, so that the dipole is set up across the complete depletion region. Because the substrate is not perfectly aligned the wells are not laterally continuous, and the etch itself is not smooth within a barrier width so it is alsopossible forcharge to be extractedalongthe wells where they are penetrated by the electrolyte. It is not possible to deduce an absolute value for the absorption coefficient from these experiments because, as equation (50) shows, photovoltage the depends upon wavelength-independent factors as suchthe depletion depth, barrier height (determines J,,) and the mechanism of carrier transportdiscussed as above. However, it is
26

Structure without Mak

v/---I 1 I
I

P
OI

$0
0 c 0

800
wavelengthlnm)

I 900

r:

I/

Gmplete structure

Figure 28. Photovoltage spectrum from the structure in figure 27. The surface photovoltage signal at680 n m is due to the electrolyte barrier with the upper GaAlAs layer and the signal from the buried GaAs junction is modulatedby p-n the transmission spectrum of theMaw. The spectrum of the same sample with theMaw structure, layers ( a ) t o ( b ) in figure 27, removed is also shown (see figure 18).

Electrochemical C-V profiling of Ill-V semiconductors

shown in figure18, and this can be used as a reference giving the spectral form of F(A)R(A)so that if the junction response is linear with intensity the absolute transmitted fraction can be obtained from apair of normalised plots as the ratio T(A)= Vl(A)/V2(A) illustrated in figure 28. It as has been shown that the spectra of TMq,(A) obtained in this way are in good agreement with the results of conventionaltransmissionspectrafromthinnedsamples (Blood 1985). This technique has been used to characterise MQW structures for studies of non-linear and bistable optical behaviour (Blood et a1 1985b, Miller et a1 1986).

Amron I 1967 Electrochem. Technol. 5 94-8 Baxandall P J. Colliver D J and Fray A F 1971 J . Phys. E: Sci. Instrum. 4 2 13-2 1 Bleaney B I and Bleaney B 1976 Electricity and Magnetism (Oxford: University Press) 3rd edn Blood P 198 1 Gallium Arsenide and Related Compounds 1980 ed. H W Thim (Inst. Phys. Conf: Ser. 56) pp 25 1-8 -1985 J . Appl. PhJS.58 2288-95 Blood P, Fletcher E D, Woodbridge K. Dawson P and Hulyer P J 1985a Gallium Arsenide and Related Compounds 1984 ed. B de Cremoux (Inst. Phys. Conf: Ser. 74) pp 427-32 Blood P and Harris J J 1984J. Appl. Phw. 56 993-1007 Blood P, Miller A and Woodbridge K 1985b Toward Semiconductor Integrated Optoelectronics(London: IEE)

Technical Digest 1985129

Blood P and Orton J W 1978 Rep. Prog. Phys. 41 157-257 Dawson P. Duggan G. Ralph H I. Woodbridge K and t Hooft G W 1985 Superlattices and Microstructures l 23 1-5 Dingle R 1975 Festkorperprobleme (Adcances in Solid State Physics) vol. 15 ed. H J Queisser (Braunschweig: Pergamon-Vieweg) pp 21-48 Faktor M M, Ambridge T, Elliott C R and Regnault J C 1980 Current Topics in Materials Science ed. E Kaldis (Amsterdam: North-Holland) vol. 6 pp 1-107 Faktor M M and Stevenson J L 1978 J . Electrochem. Soc. 125 62 1-9 Goodman A M 1963 J . Appl. Phys. 34 329-38 Johnson W C and Panousis P T 197 1 I E E E Trans. Electron Devices ED-l8 965-73 Kennedy D P and OBrien R R 1969 I B M J. Res. Dev. 13 212-4 Kimerling L C 1974 J . Appl. Phys. 45 1839-45 Klug H P and Neumann H 1976 Exp. Tech. Phys. 23 605-10 Kroemer H and Chien W Y 198 l Solid State Electron. 24 655-60 Kroemer H. Chien W Y, Harris J S and Edwall D P 1980 Appl. Phys. Lett. 36 295-7 Miller A, Steward G, Blood P and Woodbridge K 1986 Opt. Acta 36 to be published Miller G L 1972 IEEE Trans. Electron Devices ED-l9 1103-8 Missous M and Rhoderick E H 1985 Solid State Electron. 28 233-7 Pankove J I 197 1 Optical Processes in Semiconductors (New York: Dover) Redstall R M, Regnault J C and Stephenson J L 1978 Electrochem. Soc. Con$ Proc. 78-3 293 (see also Faktor et al 1980; figure 49) Rhoderick E H 1978 Metal-Semiconductor Contacts (Oxford: University Press) Schultz M 1974 Appl. Phjs. 4 225-36 Sharpe C D and Lilley P 1980 J . Electrochem. Soc. 127 1918-22 Sharpe C D, Lilley P, Elliott C R and Ambridge T 1979 Electron. Lett. 15 622-4 Stagg J P 1982 J . Appl. Phys. 53 3680-5 (his analysis follows from Hovel H J in Semiconductors and Semimetals ed. R K Willardson and A C Beer (New York: Academic) (1975) vol. 1 1 p 114) Stagg J P, Huyler P J, Foxon C T and Ashenford D 1982 J. Physique 43 suppl. 12 C5 377-82 Sze S M 198 1 Physics o Semiconductor Devices (New York: f Wiley) 2nd edn Wakefield B, Stevenson J L, Redstall R M and Ambridge T 1979 Appl. Ph.vs. Lett. 35 347-9 Whiteaway J E A 1983 I E E Proc. I30 pt I 165-70 Wiley J D and Miller G L 1975 I E E E Trans. Electron Devices ED-22 265-72 Wood C E C, Woodcock J and Harris J J 1979Gallium Arsenide and Related Compounds 1978 C M Wolfe ed. (Inst. Phqs. ConJ Ser. 45) pp 28-37 Woodbridge K, Blood P, Fletcher E D and Hulyer P J 1984 Appl. Ph.w Lett. 45 16-8

7.3. Summary
Theexperimentsdescribed in thissection show that the electrochemical profiler is valuable a tool in the characterisation of thin layerstructures.Whentheetch and depletion steps are sufficiently small it is possible to resolve quantum-well features on a scale of Q 100 A and it does seem that crater roughening is significantly reduced when etching these samples permitting resolved profiles to be recorded many over periods of the structure. The capability of recording photovoltage spectra using the standard cell is especially significant the for characterisation of MQW structures because itis a rapid method of comparing well widths, and at the same time giving data on AlGaAs composition. The method permits the absorption edge in MQW lasers to be located directly and it can be extended to obtain the absorption coefficient using suitable structures.

Acknowledgments

The work on multiple quantum-well structures described in this paper was done in collaboration with a number of colleagues, particularly K Woodbridge and J T Bellchambers who, respectively, grew the samples and gave practical assistance with the measurements. The author acknowledges also useful discussions with P Dawson G and Duggan on optical absorption and confined particle transitions. As indicated in the text, some of the work on the performance of the profiler was done by J P Stagg while at Philips Research Laboratories and his contributionto this fieldis gratefully acknowledged. Thanks are also due to T Ambridge (BTRL) for helpful conversations, correspondence and communications concerning this article.
References

Ambridge T. Elliott C and R Faktor M M 1973 J . Appl. Electrochem. 3 1- 15 Ambridge T and Faktor M M 1974 J. Appl. Electrochem. 4 135-42 -1975a J. Appl. Electrochem. 5 319-28 -1975b Gallium Arsenide and Related Compounds 1974 ed. J Bok (Inst. Phvs. ConJ Ser. 24) pp 320-30 Ambridge T. Stevenson J L and Redstall R M 1980 J. Electrochem. Soc. 127 222-8

27