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Design of a-Si:H/GaAs heterojunction bipolar transistors with improved DC and AC characteristics

F.G. Della Corte and F. Pezzimenti Abstract: Results from a detailed simulation study are presented to help evaluate the pros and cons of a wide-gap hydrogenated amorphous silicon emitter (a-Si:H) introduced to improve the injection efciency at the emitterbase junction of a GaAs bipolar transistor. For a set of devices withstanding the same maximum emittercollector voltage, it is shown that the current gain, besides a net dependence on the defect state concentration at the emitterbase interface, is also strongly inuenced by the base thickness and doping. The base thickness, however, has a weak impact on the cut-off frequency, which in turn shows a clear dependence on the emitter electron mobility. The study predicts that the current thin lm silicon technology would allow the fabrication of a transistor performing a DC current gain close to 3000 and a cut-off frequency in excess of 15 GHz. Owing to the simplicity of fabrication, such a device could represent an effective way of adding a bipolar stage to a GaAs MESFET IC without resorting to AlGaAs/GaAs heterostructures.

Introduction

n-p-n AlGaAs/GaAs heterojunction bipolar transistors (HBT) are widely used in analogue and digital appliances for wireless communication, optoelectronis and high speed computing. In fact the insertion of a wide-gap AlGaAs emitter permits fabrication of devices with a very high current gain, which is in turn traded for larger bandwidths [1]. At present, the fabrication of these devices is based on either molecular beam epitaxy (MBE) or metal organic chemical vapour deposition (MOCVD), two outstanding epitaxial technologies which, however, require expensive and hazardous equipments. As an alternative to the use of AlGaAs/GaAs heterojunctions in particular applications, recently the fabrication of GaAs-based bipolar devices taking advantage of wide-gap amorphous semiconductor regions has been considered [2, 3]. In fact, with an energy gap exceeding 1.7 eV, a-Si:H promises to allow the fabrication of high-gain HBT, while requiring a technology which is far simpler than those based on classical heteroepitaxy. Such an approach, in fact, has been already proposed and carefully discussed in the case of silicon HBTs performing an amorphous silicon (a-Si:H) or amorphous silicon carbide (a-SiC:H) emitter [47]. As a contribution to the study of possible applications of a-Si:H as a wide-gap semiconductor, in this work the DC, high frequency and switching characteristics of a GaAsbased HBT are investigated by means of numerical simulations. The device, in particular, performs an a-Si:H emitter, while the base and collector regions are made of
r IEE, 2003 IEE Proceedings online no. 20030577 doi:10.1049/ip-cds:20030577 Paper rst received 4th February and in revised form 24th April 2003 The authors are with DIMET, Mediterranea University of Reggio Calabria, Loc. Feo di Vito, I-89100 Reggio Calabria, Italy F.G. Della Corte is also with the Institute for Microelectronics and Microsystems, CNR, Via Pietro Castellino 111, I-80131 Naples, Italy

GaAs. A nite element simulator of semiconductor devices, which takes into account the distributed density of states typical of amorphous materials, has been utilised throughout the work. For careful tuning of the electronic properties of the amorphous layer, the results of a previous study, which involved the fabrication and characterisation of ad hoc devices [3], have been considered. 2 Characteristics of an a-Si:H/GaAs heterojunction

a-Si:H is known to be a highly defective semiconductor. Distortions in the co-ordination angles between Si atoms, in particular, determine the onset of additional electronic states close to the valence and conduction band limit, or Urbach tail states. Also, the lack of Si atoms in the crystal lattice produces unsaturated, or dangling, bonds which in turn introduce additional allowed states in the middle of the energy gap. The preferred deposition technique for thin lm a-Si:H is plasma-enhanced chemical vapour deposition (PECVD) in a SiH4 ambient, at temperatures of 200280 1C. In fact, this technique ensures a high degree of hydrogenation, which in turn allows a tight control over the number of gap states and the width of the energy gap [8]. In fact, depending on the deposition technique and parameters, a-Si:H can show an energy gap Eg tunable in the range 1.61.9 eV. A typical distribution of states for a-Si:H is shown, for example, in Fig. 1. Owing to the low deposition temperature allowed by PECVD, the technology of a-Si:H is compatible with that of many other semiconductors, and in particular with that of GaAs. The potential advantages of the association of these two semiconductors come from the band offsets established at the heterojunction. The two materials have in fact almost the same electron afnity, with wa-Si:H 3.93 eV [9] and wGaAs 4.07 eV. Therefore, the energy gap difference DEg is in practice completely located at the valence band side, with a valence band offset DEV of up to 0.36 eV. For the emitterbase junction of a n-p-n HBT this could in theory result in an improvement of the current gain by a
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a-Si:H emitter (n+) emitter contact base contact

tail states

conduction band

density of states

valence band

0.25 m base (p) 50 m

midgap states

0.4 m

collector (n)

energy

Fig. 1 Typical density of states (DoS) for a PECVD grown, highly doped a-SiH lm
sub-collector (n+)

factor exp(DEV/kT)E106 [1], at room temperature. In addition, due to the lack of a crystal lattice in a-Si:H, no strain exists at the interface whatever the energy gap difference, a clear advantage in comparison with AlGaAs/ GaAs heterostructures. Unfortunately, experimental works have shown that the density of states at the amorphous/crystalline interface has a negative impact on the base current of a HBT [10]. Moreover, the electron and hole mobilities in a-Si:H are very low and the resulting poor conductivity can be compensated only in part by higher doping because the doping efciency is always low in a-Si:H [8]. In an effort to gain more insight into such kinds of heterostructures, and to identify the critical aspects determining their electrical behaviour, a-Si:H/GaAs heterojunctions have been studied recently [3]. In particular the characteristics of an experimental heterojunction p-i-n diode were compared to those calculated by means of the nite element device simulator ATLAS [11], showing that limiting the number of defects located at the interface below a critical level would dramatically improve the minority carrier injection ratio at the heterojunction. Such a level, moreover, is close to that allowed by the present technology. Moving from those considerations, in this paper, the predicted DC, AC and switching characteristics of a GaAs bipolar transistor with a wide-gap a-Si:H emitter are presented and discussed for the sake of drawing some design criteria. 3 HBT structure and simulation settings

Fig. 2 Schematic representation of one half of the simulated a-Si:H/GaAs HBT

Table 1: Simulation parameters in the GaAs regions


GaAs base GaAs collector 400 1016 (n-type) GaAs subcollector 2000 5 1018 (n-type) 1, 1 1200, 60

Thickness (nm) Doping (cm3)

1450 5 1017 2 1018 (p-type) 5, 5 1200, 60

tn, tp (ns) mn, mp (cm2 V1 s1)

8, 8 8000, 400

A schematic representation of one half of the a-Si:H/GaAs HBT cell considered in this work is reported in Fig. 2. The device is in particular designed for low-power GaAs technology (VDDr5 V). The fundamental geometrical and electrical characteristics are summarised in Table 1 for the base and collector regions, and in Table 2 for the a-Si:H emitter region.

The parameters NG,C and NG,V are, respectively, the integrals over the whole energy spectrum of the two Gaussians representing the defects associated to the dangling bonds throughout the gap within the rst nanometre from the interface. Values ve times lower were considered for the same parameters in the remaining 4-nmthick part of the emitter region. This thickness was chosen to guarantee that the emitter region would not be completely depleted at the bias points of interest. Details of the defect distribution model in the a-Si:H lm are contained in [3, 12]. The a-Si:H(n) emitter stripe is 0.5 mm wide, with an emitter-to-base contact distance of 0.25 mm. To compensate for the low carrier mobility, the emitter region was assigned a doping level of 6 1018 cm3, which is close to the technological limit for a-Si:H. The base doping was changed between 5 1017 and 2 1018 cm3, with the base thickness varying accordingly between 50 and 14 nm to guarantee a base punch-through voltage of 5 V.

Table 2: Simulation parameters in the a-Si:H emitter region


Thickness (nm) 5 Doping (cm3) 6 1018 (n-type) NG,C (cm3) 3 1018 NG,V (cm3) 3 1018 mn (cm2 V1 s1) 0.1 mp (cm2 V1 s1) 0.01 Eg (eV) 1.8 wa-Si:H (eV) 4.1

Other parameters were set as in [3]


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DC analysis

The devices analysed in our simulations are listed in Table 3 with the relevant technological characteristics. For the calculation of the device terminal currents we assigned a device width of 50 mm and therefore the emitter area was 25 mm2. In addition the considered collector effective area was 75 mm2.
Table 3: Parameters characterising the various simulated devices
Device B50 WE (nm) WB (nm) NB (cm3) 5 50 5 1017 B25 5 25 1018 B14 5 14 2 1018

The current gain is shown for the three devices in Fig. 4 as a function of the emitterbase bias. In this case the defect state concentration was set to 3 1018 cm3 at the interface, a value comparable with the emitter doping level, which is known to be the major source of defects in highly extrinsic amorphous materials. With a maximum DC current gain close to 2800, device B25 shows the best trade-off between the collector efciency and the detrimental base series resistance. It is worthwhile noting that the maximum current gain is observed at an emitterbase bias of 1.3 V, corresponding to a collector current ICE103 A. Beyond this bias point, a voltage drop develops across the resistive amorphous region, determining the gradual reduction of the actual VBE fraction falling on the emitterbase junction. At lower biases, a larger carrier recombination takes place in the wider depleted portion of the base, determining a drastic decrease of the current gain.

3000

The parameters WE, WB and NB are, respectively, the emitter thickness, the base thickness and the base doping. In order to compare devices designed for the same applications, the base width was scaled in each HBT in a way such that they performed the same maximum base punchthrough voltage, i.e. VCE,max 5 V. Therefore, for each base thickness, the base doping was incremented until we observed the onset of an anomalous collector current at the xed VCE,max. To highlight the effect of the defect state concentration on the device characteristics, the DC current gain for VCB 0 was calculated as a function of the density of states at the amorphouscrystalline interface. The simulation results are shown in Fig. 3. From this analysis the effect of the interface quality on the current gain is clear. In particular, the existence of a type of threshold effect is observed, with the IC/IB ratio rapidly increasing in all devices for integral defect concentrations below 1019 cm3. This should be interpreted as a direct consequence of the improved injection efciency at the heterojunction, as was already observed in [3]. It should be noted in this connection that modern PECVD techniques allow the deposition of a-Si:H lms showing integral defect concentrations well below 1019 cm3 in the bulk of the material; less has been assessed, however, on the amorphouscrystalline interface regions.
3000 2500 2000 1500 1000 500 0 0.4 0.8 1.2 1.6 2.0 total gap state concentration NG /1019, cm3 B50 B25 B14

2500
DC

B50 B25 B14

VCB = 0

2000 1500 1000 500 0 0.4 0.8 1.6 1.2 base voltage VBE , V 2.0 2.4

Fig. 4 DC current gain as a function of the emitterbase bias for the three simulated devices

Device B25 shows the best DC characteristics. In fact, while device B50 suffers from an excessive recombination in the wider depleted portion of the base, device B14 is penalised by a poorer emitter junction injection efciency as an effect of the higher base doping. In Fig. 5 the Gummel plots are shown for device B25 calculated at two different interface defect concentrations. The two devices perform comparable current gains.
0 2 current IC, IB, 10X A 4 6 8 10 12 14 0.4 0.8 1.2 base voltage VBE , V 1.6 2.0 NG = 2 1018 cm3 NG = 7 1018 cm3

current gain,

DC

Fig. 3 DC current gain as a function of the total gap state concentration at the amorphouscrystalline interface
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Fig. 5 Gummel plot for device B25 calculated at two different interface defect concentrations
Base and collector are held at same potential
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current gain,

However, at the low biases the base current is dominated by the recombination taking place in the base region of the electrons injected from the emitter; as a better interface allows a more efcient injection, a higher recombination follows with respect to the more defected heterojunction. This effect is clearly seen in Fig. 5, where for VBEo0.9 V a higher base current is observed for NG,C NG,V 2 1018 cm3. By raising the base bias, the interface recombination is increased with respect to the base recombination. This effect is obviously more prominent in worse interfaces, resulting in an enhancement of the base current and a lowering of the device current gain. 5 AC and switching analysis

The parameter S21, representing the voltage gain for matched load, is higher than 12 dB for all the devices at low frequencies. The gain drops to unity at 9 GHz for device B14, 8 GHz for device B25 and 7 GHz for device B50; these frequencies are therefore the respective maximum oscillation frequencies. In the same frequency interval the device transconductance was also calculated as shown in Fig. 7. It drops from 430 mS/mm, at low frequency, to 240, 195 and 165 mS/mm, respectively, for devices B14, B25 and B50, at about 10 GHz. Once again the maximum oscillation frequency of 9 GHz calculated for device B14 slightly differs from that of the 50 nm thick base device B50.
500 transconductance gm , mS/mm B50 B25 B14

400

Small signal analysis of the devices B50, B25 and B14 was performed to assess their high-frequency behaviour. Proceeding from a DC solution at an assigned bias, the simulator applies a frequency-swept AC generator to the base contact, with the device used as a common emitter amplication stage. We focused our attention on the small signal current gain bAC, the transconductance and the scattering parameter S21. The short circuit AC current gain bAC was calculated with the devices biased in the active region, namely with VC 3 V, VE 0 and VB ramping from 1.0 to 2.0 V. The quite large emitterbase polarisation is necessary to sustain a base current IB parallelly ramping from 109 to 104 A. As an example, the simulation results for VB 1.6 V are shown in Fig. 6 for NG,C NG,V 3 1018 cm3. The three plots are in fact coincident; for all of the devices the low frequency bAC is close to 50 dB, while the cut-off frequency ft is approximately 8 GHz. This substantial equivalence is an unusual result for bipolar transistors if one considers the progressive base thinning from 50 to 14 nm, and demonstrates that the base transit time gives a minimal contribution to the overall emittercollector transit time. In fact, the factor that actually limits the high-frequency performances of these devices is the emitter junction transit time, which in turn is kept high by the large resistance. We calculated, in fact, that the emitter differential resistance re is in excess of 60 O, while common values in standard GaAs HBTs are generally in the range of a few ohms. This result further enforces the theory that extremely thin emitters are fundamental in amorphous/crystalline heterojunction bipolar devices.

300

200

100

0 0 2 4 6 frequency, GHz 8 10

Fig. 7 Calculated frequency dependence of the transconductance gm for the three described devices

The device high-frequency characteristics are obviously affected by the quality of the amorphous layer. Table 4 summarises the calculated cut-off frequencies ft for device B25 for various electron mobilities and for two defect state concentrations, namely 1018 and 3 1018 cm3. The simulations demonstrate that the cut-off frequency is remarkably sensitive to the electron carrier mobility, while we observed no dependence on the hole mobility, which was therefore xed at 0.1 cm2 V1 s1. It should be noted, in addition, that the mobility values considered in this analysis are consistent with those reported for good quality a-Si:H lms or standard mc-Si:H (microcrystalline) lms. A minor impact on the AC performances is conversely shown by the defect concentration.
Table 4: Calculated maximum cut-off frequencies

60 dB 50 40 30 20 10 0 B50 B25 B14

Device B25

Mobility (cm2 V1 s1) mn 0.1, mp 0.01 mn 0.2, mp 0.01 ft 16 GHz mn 0.5, mp 0.01 ft 30 GHz

AC ,

small signal current gain,

NG,C NG,V 1018 cm3 NG,C NG,V 3 1018 cm3

ft 8 GHz ft 7.5 GHz

ft 15.2 GHz ft 29 GHz

10 107 108 109 frequency, Hz 1010 1011

Fig. 6 AC current gain of devices B50, B25 and B14 at a base bias VBE 1.6 V
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To evaluate the switching behaviour of the device, transient time simulations were performed while forcing device B25 to pass through the off-on-off states. The step signal shown on top of Fig. 8 was applied to the base contact, while the collector current through a 50 O load resistance or the collector potential, also shown in Fig. 8, were monitored. The characteristic switching times are listed in Table 5, where ton, toff and ts are, respectively, the switchon, switch-off and storage time, while tpLH (tpHL) is the
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2.5 base voltage, V 2.0 1.5 1.0 0.5 0 6 collector voltage, V 5 4 3 2 1 0 1 0 0.5 1.0 1.5 time, ns 2.0 2.5

interface quality, which has a severe inuence on the junction injection efciency. The current gain in particular rapidly increases for defect concentrations below 1019 cm3. The calculated AC parameters have revealed a minimal dependence on the base thickness, and therefore on the base transit time. In fact, the factor that actually limits the highfrequency performances of these devices is the emitter junction transit time, which in turn is kept high by the large emitter resistance. The cut-off frequency is, however, strongly dependent on the amorphous layer electronic properties, and in particular on the carrier mobility. A cutoff frequency in the range 15 to 30 GHz is predicted in a device with optimised base width and doping, if the emitter electron mobility is assumed to be in the range 0.2 to 0.5 cm2/s. An average propagation delay of 125 ps has been nally calculated. 7 Acknowledgments

Fig. 8 Transient time simulation of the switching response of device B25


Signal on top is applied to the base while a 50 O load is present on the collector

Simulations were performed at the Institute for Microelectronics and Microsystems of CNR, Naples, Italy. 8 References

Table 5: Characteristic switching times for device B25


ton 90 ps toff 310 ps ts 140 ps tpHL 70 ps tpLH 180 ps

propagation delay measured between the instants where the input and the output signals are at 50% of their respective evolution, with VC going from low to high (high to low). These values demonstrate that in spite of the presence of the amorphous layer, the charge accumulation and extinction processes are controlled by the carrier lifetime in the GaAs base. It should be noted that a similar conclusion has already been reported, drawn from experimental measurements carried on a-Si:H/GaAs p-i-n devices [13]. 6 Conclusions

The impact of some geometrical and technological parameters on the DC, AC and switching characteristics of aSi:H/GaAs n-p-n HBTs has been analysed through numerical simulations, duly taking into account the gap states in the amorphous semiconductor emitter. The analysis has demonstrated that the device DC characteristics are strongly dependent on the amorphous/crystalline

1 Kroemer, H.: Heterostructure bipolar transistors and integrated circuits, Proc IEEE, 1982, 70, pp. 1325 2 Mimura, H., and Hatanaka, Y.: Electrical properties of p-type amorphous silicon-n-type crystalline gallium arsenide heterojunctions, Jpn. J. Appl. Phys., 1985, 24, pp. 355357 3 Della Corte, F.G., Rubino, A., and Cocorullo, G.: Simulation study and realisation of an a-Si:H emitter on GaAs, Solid-State Electron., 1998, 42, pp. 18191825 4 Orpella, A., Bardes, D., Alcubilla, R., Marsal, L.F., and Pallares, J.: In situ-doped amorphous Si0.8C0.2 emitter bipolar transistors, IEEE Electron Device Lett., 1999, 20, pp. 592594 5 Li, P., Li, Y.Q., and Salama, C.A.T.: A heterojunction bipolar transistor with a thin a-Si emitter, IEEE Trans. Electron Devices, 1994, 41, pp. 932935 6 Sasaki, K., Rahman, M.M., and Furukawa, S.: An amorphous SiC:H emitter heterojunction bipolar transistor, IEEE Electron Device Lett., 1985, 6, pp. 311312 7 Symons, J., Ghannam, M., Neugroschel, A., Nijs, J., and Mertens, R.: Silicon heterojunction bipolar transistors with amorphous and microcrystalline emitters, Solid-State Electron., 1987, 30, pp. 1143 1145 8 Street, R.A.: Hydrogenated amorphous silicon (Cambridge University Press, Cambridge, 1991) 9 Matsuura, H., Okuno, T., Okushi, H., and Tanaka, K.: Electrical properties of n-amorphous/p-crystalline silicon hetero-junctions, J. Appl. Phys., 1984, 55, pp. 10121019 10 Bonnaud, O., Sahnoune, M., Solhi, A., and Lhermite, H.: Modeling the base current of an a-Si:H/c-Si heterojunction bipolar transistor, Solid-State Electron., 1992, 35, pp. 483488 11 Silvaco Int.: Atlas device simulation software users manual V.5.0.0.0.R (Silvaco Int., Patrick Henry Drive, Building 1, Santa Clara, CA, USA, 1999) 12 Della Corte, F.G.: Simulation Study of the DC and AC characteristics of an a-Si:H(n)/GaAs(p)/GaAs(n) heterojunction bipolar transistor, Solid-State Electron., 2000, 44, pp. 22652271 13 Della Corte, F.G., Polichetti, T., Rubino, A., and Cocorullo, G.: Study of a-Si:H emitters for efcient carrier injection in GaAs bipolar devices, J. Non-Cryst. Solids, 2000, 266269, pp. 10491053

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Study of electroluminescence in porous silicon for sensing applications


A. Tsargorodskaya, A.V. Nabok and A.K. Ray Abstract: Electroluminescence (EL) of porous silicon (PS) samples was studied at anodic polarisation using neutral electrolyte contact. SEM and AFM morphology study of PS revealed its complex structure comprising features with micrometre and tens of nanometre dimensions. The observed features of EL, including its degradation during anodisation, were discussed in terms of a phenomenological model of a chemically modied silicon surface. The adsorption of polyelectrolytes polyallylamine (PAA) and polysterylsulphonate (PSS) demonstrated sufcient improvement of EL stability. The effect of adsorption of protein bovine serum albumin (BSA) on EL quenching was studied.

Introduction

The large surface area of porous silicon (PS) has stimulated recent interest in its applications for sensor development. Due to a very high concentration of adsorption sites on the PS surface, the sensitivity of PS transducers to molecular adsorption can be increased by two orders of magnitude over that of two-dimensional transducers. This approach has become popular in recent years, and several experimental attempts have been made to study molecular adsorption and to perform different chemical and biochemical reactions in the PS matrix [16]. Several physical principles were exploited in PS transducers, namely, optical FabryPerot interferometry [7], ellipsometry [8], photoluminescence (PL) [9] and electroluminescence (EL) [10]. The latter seems to be the most attractive because it combines the high sensitivity of luminescence measurements with the much easier and cost-effective method of its excitation as compared to PL. Moreover, EL can be performed by simple measurements of emitted light intensity at a xed wavelength. Yet the use of an electrolyte contact in EL measurements allows easy operation with chemical and bio-reactions in the aqueous phase. The main phenomenon to be exploited in PS transducers is the quenching of the luminescence due to molecular adsorption and some products of chemical reactions [3, 9, 11]. However, the main drawback of both PL and EL methods lies in the poor stability of the light emission, which decays rapidly due to a number of external factors, such as temperature, electric eld, strong illumination and electrochemical reactions [1214]. Another important issue of PS is the reproducibility of its main characteristics and the luminescence in particular. At present, despite a large number of publications on this topic, the formation of PS with desirable properties is still a subject of intense scientic
r IEE, 2003 IEE Proceedings online no. 20030640 doi:10.1049/ip-cds:20030640 Paper rst received 28th February and in revised form 1st May 2003 The authors are with the Nanotechnology Research Laboratories, Shefeld Hallam University, School of Engineering, City Campus Pond Street, Shefeld S1 1WB, UK IEE Proc.-Circuits Devices Syst., Vol. 150, No. 4, August 2003

pursuit. The mechanism of PL in PS is not nally established. There exist ve or six different physical models explaining some particular features of PL and EL, but they are not universal since there are a number of experimental facts contradicting those models [12]. Some experimental work towards immunosensing has been done recently using the PL in PS [3,9,11]. In particular, it was shown that the absorption of immune components in PS and the following immune reactions affect the intensity of PL. Much less work has been done so far on the application of EL for chemical and bio-sensing. The present study targets the improvement of the reproducibility and stability of EL in PS, further development of the physical model of EL and the exploitation of EL for chemical and bio-sensing. The latter narrowed the choice of the electrolyte for this work. Instead of using redox electrolytes and cathode luminescence, which can provide high light emitting efciency and stability [12], we performed anodic EL in neutral electrolytes, such as trizma buffer, compatible with proteins. 2 Experimental

2.1

Preparation of porous silicon

Porous silicon (PS) layers were prepared by a standard method of anodisation of n-type /100S Si wafers of resistivity in the range of (4.510) 102 O m in electrolyte containing hydrouoric acid [15]. The experimental set-up used for the PS formation is sketched in Fig. 1. Silicon samples were sealed against the PTFE electrochemical cell through a rubber O-ring, so that the front side of the silicon wafer was in contact with the electrolyte. In the case of n-type silicon, holes necessary for pore formation were generated by illuminating the front side of the sample with a 300 W solar simulator lamp. In order to provide uniform electrical potential and thus homogeneous current density across the sample, the back sides of the silicon wafers were coated with silver conductive paint. The electrical contact between the Si wafer and a power supply was provided via a metal ring. The counter electrode was a platinum spiral immersed in the electrolyte. The electrolyte was prepared by adding 49% HF to the (1:1) ethanol/water mixture up to a desired concentration of about 21%. The anodisation of the Si surfaces was carried
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power supply PTFE container

Results and discussion

3.1

Structural characterisation of PS samples

Pt electrode light source silicon substrate plastic window electrolyte metal ring

PS samples with different pore sizes and shapes were obtained depending on the type of silicon and the parameters of electrochemical etching. Figures 2 and 3 depict typical SEM and AFM images of porous silicon layers. Typically, PS samples have a complex morphology combining pores in micrometre and tens of nanometre dimensions. The image in Fig. 2a shows a fractal structure with islands separated by at cross-shaped sections. The latter contain smaller pores visible as dark crosses and having the same orientation as the large ones (see also Fig. 2a). The formation of pores of this shape is presumably caused by selective electrochemical etching of the /100S Si

Fig. 1

Set-up for the formation of porous silicon

out at positive DC bias applied to the Si electrode with a current density of about 400 A m2. The etching time usually lasted no longer than 15 min. Following anodisation, the samples were rinsed with Millipore water for 10 min and then in a stop-solution (acetone or ethanol) for 57 min, and nally dried with nitrogen. The resulting PS samples had a circular shape with an area of about 2.5 104 m2.

2.2

Experimental methods

The morphology of PS samples was studied by scanning electron microscopy (SEM) and atomic force microscopy (AFM). The Philips XL40 ASEM/EDS instrument was used, with typical accelerating voltages of 1020 kV. The AFM study was carried out using the Nanoscope IV instrument equipped with Si3N4 tips of 4 nm radius. The AFM pictures of the PS samples were obtained in a tapping mode and at a slow scan rate of about 0.10.2 s1. The latter was chosen because of the high surface roughness of PS samples previously observed by SEM at a larger scale. The electroluminescence measurements were performed in a specially designed cell of 2 107 m3 in volume having a transparent window and two (inlet and outlet) tubes to allow the injection of different solutions into the cell. A metal syringe needle, serving as one of the tubes, provided electrical contact to the electrolyte. PS samples were sealed against the cell through the rubber O-ring. Typically, an aqueous solution of 35 mM/l trizma-base/HCl buffer (pH 7.35) obtained from Sigmas was used as an electrolyte. All EL experiments were carried out at room temperature at variable (315 V) positive (anodic) bias applied to the Si electrode. EL spectra were registered in a wavelength range of 3001000 nm using the Spex 1681 monochromator and a CCD detector. The EL kinetics experiments were performed in situ at a xed wavelength of 633 nm using the Anritsu ML 9001A optical power meter. The effect of adsorption of bovine serum albumin (BSA) from Sigmas, as a common protein, was studied by measuring the EL kinetics in response to consecutive injections into the cell of pure trizma/HCl buffer and the buffer containing 1 mg/ml of BSA. EL kinetics measurements were also deployed to study the effect of adsorption of polyelectrolytes, namely polyallylamine hydrochloride (PAA) and polysterylsulphonate sodium salt (PSS), both purchased from Aldrich. 2 mg/ml solutions of both PAA and PSS in millipore water were used.
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Fig. 2

SEM images of porous silicon

a, b Top views of different fragments of PS surface c Cross-section view of cleaved PS/Si sample
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Digital Instruments NanoScope Scan size 5.000 m Scan rate 0.2001 Hz Number of samples 512 Image Data Height Data scale 150.0 nm

view angle light angle

3 4 m

0 x 1.000 m/div z 150.000 nm/div

Fig. 3

AFM image of nanoporous section of PS


330 s 510 s 800 EL intensity, a.u. 600 400 200 0 400 1140 s 270 s 180 s 780 s

surface in the [001] and [010] directions. The image zoomed in on the island top shows nanoporous sponge structure (Fig. 2b), which was conrmed independently with AFM (see Fig. 3). The pores size in the range of 0.050.5 mm was evaluated from those images. The cross-section SEM image, presented in Fig. 2c, allows the evaluation of the pore depth, and thus the thickness of the PS layer. Mean values of the pore size and depth for different samples are summarised in the Table 1. The porosity of the PS layers was estimated to be 78% using a gravimetric method [12, 16].
Table 1: Average pore size and depth for PS samples (SEM/AFM data)
Morphology features Islands Big crosses between islands Small crosses Sponge structure on top of the islands Pore size, mm B10 (Fig. 2a) 625 (Fig. 2a) 12 (Fig. 2a) 0.50.05 (Fig. 2b, Fig. 3) 717 (Fig. 2c) Pore depth, mm

1000

500

600

700

800

900

1000

wavelength, nm a 1200 1000 EL intensity, a.u. 800 600 400 200 1.6 1.7 1.8 EL peak position, eV

3.2 General features of EL and the model of the modied surface of PS


A typical set of anodic EL spectra measured in trizma/HCl buffer at 7 V applied to a Si electrode is presented in Fig. 4a. Changes in both the intensity and peak position of EL during the course of anodisation are shown in Fig. 4b. At the very beginning (up to 300 s) of anodisation the EL intensity is found to slightly rise along with a small blue shift of the EL band, but the intensity decreases subsequently accompanied by the red spectral shift. The transformations in the EL peak depending on the bias voltage are shown in Fig. 5. Here the luminescence intensity increases with the voltage increased from 7 to 12 V, and this is accompanied by a very small blue shift of the EL band of about 5 nm. Observed features of EL spectra are different from the results reported earlier in [17, 18]. In those works EL spectra measured at different voltages enveloped in the PL
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0 0 500 1000 time, s b 1500 2000

0 1.5

Fig. 4

EL Properties of PS

a EL spectra of PS as a function of anodisation time shown near respective curves b Time dependencies of the intensity and peak position of EL

spectrum were explained reasonably well in terms of the PS model having a wide size distribution of nanocrystallites (nanowires) and thus the band gap varied from 1.32.0 eV [17]. In that case, a larger applied voltage is expected to tune the electron transfer to smaller nanocrystals causing a blue shift of the EL band.
357

40

12 V

30 EL intensity, a.u. 9V 20 7V 10

0 400 500 600 700 wavelength, nm 800 900 1000

Fig. 5

EL spectra of PS as a function of anodic bias voltage

In our experiments the observed energy blue shift of the EL band of about 10 meV is much smaller than that expected from the above model. Additionally only the
Si siloxane

crystallites with size of 35 nm would result in a sufcient increase in the band gap [19]. According to our morphology study, PS contains nanocrystals of about an order of magnitude larger, which is supposed to produce a negligible effect on the band gap. The luminescence in the visible range was observed earlier in mesoporous PS samples having crystallites of submicron dimensions [12]. This means that the presence of silicon crystals of a few nanometers in size is not essential for the luminescence in the visible range. A model illustrated by Fig. 6 is proposed for the explanation of observed features of electroluminescence. First, it is assumed that the size of PS crystallites is not small enough to provide quantum connement conditions and thus to increase the band gap. Secondly, the surface of porous silicon contains a large number of siloxane (SHO) groups which form a thin siloxane surface layer and can be represented by characteristic HOMO and LUMO bands [20]. In fact, it is difcult to distinguish between siloxane levels and the surface states of other origin, so that the
electrolyte H+/H (2.5 eV)

HOMO CB (4eV)

1.5 1.7 eV 1.1 eV

VB LUMO O2/O (7 eV)

e O2/O e O2/O

h1 h2 < h1

h+

h+

Fig. 6

Energy band diagrams of PS/electrolyte contact

a At zero bias (positions of energy levels are shown in respect to the vacuum level) b At anodic bias application c After anodic oxidation of PS surface
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surface of PS can be represented by a large concentration of surface states covering a wide energy range. Another consequence of having a large density of surface states is that the Fermi level is most likely pinned on the surface, and any external charge (due to external bias) will be screened by recharging the surface states. In general, a partial screening by the semiconductor space charge, and thus a small band bending, may take place (see Figs. 6b and 6c). However, this would not change dramatically the proposed energy band model. When no external bias is applied, the two nearest redox energy levels in the electrolyte O2/O and H+/H are lying below the valence band and above the conduction band edges, respectively (see Fig. 6a) [21]. The application of a relatively small external bias, which is just enough to match the O2/O level with the valence band edge, will cause anodic oxidation of Si with holes supplied through the valence band. However, there is no luminescence in this case. To observe luminescence a large positive bias (of 5 12 V in our experiments) is required in order to match the O2/O level with the LUMO siloxane band on the Si surface (Fig. 6b). In such conditions, the injection of electrons from the O2/O level to the HOMO level takes place followed by an allowed electron transition between HOMO and LUMO siloxane bands and photon emission, e.g. luminescence. The energy of the emitted photon depends on the applied voltage but is limited by the relatively narrow HOMO band. The above process is, however, accompanied by anodic oxidation of silicon. The voltage drop on that oxide layer causes lowering of the O2/O level and therefore a decrease in the emitted photon energy (see Fig. 6c). This explains the red spectral shift of the EL band in our experiments. Also the presence of an oxide layer reduces the current through the contact and thus the injection of carriers and luminescence intensity.

The idea of stabilisation of the surface of PS by its chemical modication [22] was further developed here by using adsorption of polyelectrolytes. Both types of polyelectrolytes, e.g. polycationic (PAA) and polyanionic (PSS), are supposed to form strong Coulomb bonding with the PS surface containing both OH and H+ groups as respective binding centres. The absorption of both PAA and PSS has resulted in extended EL lifetime, as seen from the results of EL kinetics measurements at a xed wavelength of 633 nm in Fig. 8. For this particular sample, the decay time of EL increases from 120 s for untreated PS to 540 s for PS having adsorbed polyelectrolyte layers. It should be noted that unlike PAA, the adsorption of PSS causes substantial reduction in EL intensity (see Fig. 8). The most likely reason for such behaviour is the passivation of the PS surface with polyelectrolytes. The adsorption of a negatively charged PSS polymer chain causes repelling of O2 ions from the surface and thus the reduction in electron injection and luminescence.
1.6 EL intensity, a.u. ( 1010)

1.2

(ii)

0.8

(i)

0.4

(iii)

0 0 60 120 180 240 300 360 420 480 540

time, s

Fig. 8

EL kinetics measured in different solutions

3.3 Effect of molecular adsorption on electroluminescence


The effect of adsorption of BSA molecules on EL spectra is shown in Fig. 7. The consecutive EL spectra were measured in pure trizma/HCl buffer and the solution of BSA in trizma/HCl. The reduction in EL intensity occurred at each exposure to BSA on the background of the gradual decay of EL possibly due to anodic oxidation of PS. It is believed that BSA molecules interact with the siloxane surface of PS and partially block the electron transfer to PS and therefore cause the reduction in EL.
500 1 400 2 EL intensity, a.u. 300 4 3

(i) 35 mM/l trizma/HCl (ii) 2 mg/ml aqueous solution of PAA (iii) 2 mg/ml aqueous solution of PSS

The presence of PAA on the surface of PS improves the stability of the EL response to adsorption of BSA, which can be seen from Fig. 9 representing the EL kinetics as a response on consecutive exposures to pure trizma/HCl buffer and 1 mg/ml solution of BSA in trizma/HCl. The drops in EL signal are due to changes of the solution and also correspond to the empty cell. BSA molecules, which are negatively charged at pH 7.35, interact well with the

3.0 EL intensity, a.u. ( 1010) 2.5 2.0 1.5 1.0 0.5 0 trizma PAA BSA BSA trizma trizma trizma

200

100

0 400 500 600 700 800 900 1000

wavelength, nm

120

240

360 time, s

480

600

720

Fig. 7 Series of consecutive EL spectra measured in pure 35mM/l trizma/HCl buffer (1, 3) and 1 mg/ml solution of BSA in trizma/ HCl (2, 4)
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Fig. 9 EL kinetics: the effect of consecutive exposures to solutions of PAA, trizma/HCl and BSA
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positively charged PAA layer. It should be also noted that a dramatic increase in EL intensity during exposure to PAA solution is simply caused by the presence of Cl counter ions having a higher redox energy level than that for O2/O. A nearly similar effect on EL was observed when NaCl solution was used as an electrolyte. In contrast to results shown in Fig. 9, adsorption of BSA on PSS should not happen since both components are negatively charged. That is why the EL kinetics in Fig. 10 do not show a noticeable difference between the response to trizma/HCl buffer and BSA.

Acknowledgments

The authors are grateful to Material Research Institute, Shefeld Hallam University for the use of their experimental facilities (SEM and AFM). Thanks are due to Dr. M. Simmonds (MRI, SHU) for his help with AFM measurements and J. Hill (The University of Shefeld, Physics Department) for EL spectral measurements.

6
1.50 PSS 1.25 EL intensity, a.u. ( 1010) BSA 1.00 trizma 0.75 0.50 0.25 0 0 120 240 360 480 time, s 600 720 840 960 trizma trizma BSA trizma BSA

References

Fig. 10 EL kinetics: the effect of consecutive exposures to solutions of PSS, trizma/HCl and BSA

Conclusions

The samples of porous silicon produced for electroluminescence study of molecular adsorption were investigated with SEM and AFM methods, and the morphology revealed the presence of pores having a wide range of dimensions from micrometres down to tens of nanometres. EL measurements were performed at the anodic polarisation of PS in neutral aqueous electrolytes, such as trizma/HCl or NaCl, which can be useful for bio-sensing. The observed features of EL cannot be explained in terms of the most common model of Si nanocrystallites having band gap enlargement due to quantum connement [12]. Instead, the model of the Si surface, chemically modied with siloxane groups [20] resulting in a very high concentration of surface states, was successfully applied in our case. EL was found to be unstable and rapidly decaying due to anodic oxidation of PS in aqueous electrolytes. The problem of EL stabilisation has to be addressed before proceeding with further chemical sensing research. It was shown here, that the adsorption of polyelectrolytes on a PS surface substantially improves the stability of EL and makes this method more suitable for chemical and bio-sensing. It was shown that adsorption of BSA molecules, as an example of common proteins, caused reversible quenching of EL. Since such adsorption is not selective and other biomolecules may cause a similar effect, further work on PS biosensors will be focused on the investigation of highly specic bioreactions, such as antibodyantigen binding, using EL as an analytical tool. Such work towards the development of PS immune EL sensors is currently underway.

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