Pra i Great Brine Al Shs mer Covi 18° aesan ul PHOTOELECTROMAGNETIC EFFECT IN SEMICONDUCTORS AND ITS APPLICATIONS, M. NowAK. Institute of Physics, Silesian Technical University, 4-100 Gliwice, Poland CONTENTS Notation 1, Introduction 2. General Formulation 21" Basic equations ofthe phenomenological theory ofthe PEM effect 22. Theory of the PEM eflect in an isotropic, homogeneous semiconductor in the case of steady ‘Mumination 3, Dependence ofthe PEM Effect in an Isotropic, Homogeneous Semiconductor on Experimental Variables SIP Spectral dependence ofthe PEM effect SILL Impunty PEM eflect 4312 Radiative electromagnetic effect 32. Dependence of the PEM elect on magnetic field 321 Second order PEM effect 33. Dependence of the PEM effect on polarisation, angle of incidence, an intensity of radiation 331. PEM effect under high illumination conditions 34. Transient PEM effect 435, Field assisted PEM effect 36. Dependence of the PEM effect on recombination parameters and concentration of carvers in a semiconductor M6 37. Influence of sample dimensions on the PEM effect 29 4. PEM Effect in Anisotropic or Inhomogeneous Semiconductors 254 41. PEM eflect in anisotropic semiconductors Dot 42. PEM eflect in semiconductors with near-surface layer space-charge and in planar p-n semiconductor structures 286 43. Bulk PEM eect, 260 44. PEM effect in graded energy gap semiconductors 261 45, PEM effet on p-n junctions and in samples with anomalously high photovoltages 268 46, PEM effect in semiconductors with metalic inclusions an 5. PEM Effect at Low Temperatures and in Strong Magnetic Fields m PEM effect of ot earirs m S111, Dependence of the PEM effect on photon energy in the case of hot caries 24 5112. Kafluence of radiation intensity, magnetic field and temperature on the PEM effect of hot carriers 216 52. PEM eflect in quantsing magnetic elds ms 521, Shubnikov-de Haas orilations in the PEM elect 29 522 Magnetophonon osilaions in the PEM efect 280 523, Influence of magnetoabsorption on the PEM effect 281 524 Magneto-impurity osilations in the PEM eflect, 282 6, PEM Methods of Determining Semiconductor Parameters 212 6.1. Estimation of semiconductor pacameters using the absolute values of PEM responses: thick-slab method 2s 62. Methods using spectra distribution of the PEM response 216 621. Spectral investigation ofthe PEM effec in the range of relatively strongly absorbed radiation 286 622 Method J, 3 Tu (623. Method based on the change of sgn of the PEM sign 28 624. Nomerical fitting ofthe spectral dependence of the PEM effect 288 63, Methods based on the magnetic eld dependence of the PEM eflect and on the ld assisted PEM fect, 230 631, Kurnick-Zitter method 230 4632. Numerical fiting ofthe dependence of PEM effect on magnetic fekd 2 4633, PEM investigation of semiconductors in quantising magnetic fields 24 ‘634, Field assisted PEM method of semiconductor investigation 235 ores save 208206 M. Nowax: 64. Polarisation and angular methods of PEM investigation 29s 664.1. Investigation ofthe spectral dependence ofthe ratio of PEM responses for variously polarised radiation 27 1642. Comparison of PEM responses measured for opposite-sideiluminations ofa sample 297 65, PEM investigation of strongly illuminated samples 238 66, Methods based on the transient PEM effect 30 ‘66:1. Investigation ofthe PEM effect inthe case of plsed illumination 300 4662. High-frequency method of PEM inves 30 63. The phase diference method 301 167. Methods based on the comparison between exposes of PEM and other photoefects 303 671, PEM-PC ratio method 304 672. PEM-PC compensation method 306, 673. Comparison of PEM response with photovoliage between font and back sample surfaces 307 674. Comparison betwees the tt and second order PEM responses 308 {68 Estimation of semiconductor parameters using contactless methods of PEM investigation 309 69. PEM methods for determining parameters of inhomogeneous semiconductors BI 669.1, Methods using bulk PEM effect investigation 313 69.2. PEM investigations of graded energy gap semiconductors 3a 69.3. PEM methods of investigation of semiconductor layers with anomalously high photovoltages 315, 694, PEM methods for determining parameters of semiconductors with metalic inclusions a6 610, PEM methods of determining parameters of anisotropic semiconductors 37 6.101. PEM-PC ratio method for variously oriented samples of anisotropic semiconductors ay 6.102. Comparison ofthe PEM response and transverse Dember photovolage 318 7, Photoeletromagnetic Detectors of Infrared Radiation 319 TL. Parameters of PEM detectors 221 72. Influenes of photoelement parameters on the pesformance of IR-PEM detectors 32 73. “Dead temperature” for PEM detectors 326 7. Comparative performance of PEM detectors 309 8. Photomagnetometers 330 9. Final Remarks 331 References 332 Appendix I, Index of Papers in which the PEM ifect was Used for Determining Parameters of Various Semiconductors sar NOTATION value of the effective refractive index, see Ega (29) — detector sensitive area receiving the IR radiation ‘vector of magnetic field induction ‘Value of magnetic feld induction BPEM bulk PEM effet velocity of light in free space >d Aambipola cartier diffusion constant, sce Eqn. (221) D,.D, —difusion coastants for electrons and holes o ‘normalised detectvity of 2 PEM detector e abolute valu of electric charge emf electromotive free E ‘sector of electric Held intensity E,.Ey internal efletive electric ds for electrons and holes, see Eqns (46) and (4.7) Ey ‘alue of elective energy iansferted from photogenerated clectrons tothe free carrier sytem z ‘alte of enerey enn Enc ~opemcreuit PEM elect field Ee fper-creut PPM electric fed saturated with high intensity illumination of a sample EXE, top of the valence hand and bottom of the conduction band gz electric field vntensity in PC oF fel assisted PEM investigations f —requency ofthe measured PEM response Jose modulation fequencice of radiation intensity and magnetic eld induction ay ‘bandwidth ofthe measured signal In) spectroscopic splitting factor GF Gurevich Fusov {magnetophonon) magnetoquantum osilations Gq.Gy photoeneration rates for electrons and holes ‘AGG —photoconductance and dark conductance ofa sample i Planck's constant fe urtent flowing through a sample in the case of the compensation of PEM by photoresistive voltage ‘radiation intensity (in photons)Photoelecromagnetc effect in semiconductors 207 len Fe Hek Uns Tye tg) vectors of electron and hole current densities i “intensity of radiation incident upon a sample Ine imensity of the PC current Troe, Ine, Irp~short-cireuit currents evaked by PEM, PV, and transversal Dember eft, respectively Tyee. Ty, intensity (in photons) of plane-polarised radiation entering sample. Index v replaced by p of s represents the cases of plane-polarised radiation with electric vector in and normal to the plane of incidence infrared radiation ordinary and efletive optical absorption coeficens, see Eqn. (28), Boltzmann constant dimensionless absorption coeficint thickness of the space-charge layer near semiconductor surface “length and width of @ sample (dimensions of the illuminated sample surface) elective ambipolar cari difasion length which is determined in PEM investigations, see Eqn. (219) imf.mt effective masies of eletrons and holes " vector normal 10 the front surface of a semiconductor 11 ma. mq—al puts of radiation refractive indices of the semiconductor and the sample substrate ne —eal part of semiconductor refractive index. Indices p and s represent the cases of plane-polarised radiation with the electric vector perpendicular and parallel tothe external magnedc feld B ry Mas My —*eftactive indices ofthe medium, in which there isthe investigated structure, and ofthe coating layers fom the front and back semiconductor surfaces ess ite Am—concentrations of equilibrium and ences electrons and holes n “carrier concentration in an intrinsic semiconductor Number of p-n junctions in a sample N-E —Nernst-Ettingshausen (fees) NEL —nosse equivalent input NEP —noise equivalent power NGS narrow gap side of graded energy gap structure Pc hotoconductivity PEM —photoslctromagnetic PEM-MJ—PEM effect ina sample with moltple p-n junctions PTME —photothermomagnetoeleetic Pv Photovoliae 4g —_—Surface adhesion factor for carriers Qa —Nernst coefficient Fan Fas toe modules of effective Fresnel coefcients of internal refection of radiation from front and back ‘Stmiconductor surfaces. Indices p and $ have the same meanings as for Ty and ly ® coeficient given by Eqn, (218) ar ‘change of sample resistance evoked by illumination Ry —sample ressiity in the PEM investigation RL, R, —tecombinaion rates for electrons and holes Ry Hall coeicient Ry —_—voltage responsivity of a PEM detector Ruz —tolal responsivity ofa PEM detector illuminated by a blackbody radiation source wit temperature T “yin. Ss Say Fecombination velocities atthe Front and back sample surfaces for electrons and holes WL La sywnyl 2, Sm sywrsL t= syutyl-?—dimensionless front and back surface recombination velocities s ‘lective surface recombination velocity of carriers SH —Shubnikov-de Haas magnetoguantum oscil SIN — signal-to-noise ratio T femperature Ty —latice temperature ofthe investigated sample AT —dliference Between electron temperature and latice temperature on the front surface of «sample Ty, T_— —squares of modules ofthe effstive Fresnel coeficients of radiation transmission across the front surface ofa semiconductor. Indies p and s have the same meanings a fr Jy and ly Ux current voltage drop on the illuminated part of a sample in the ease of compensation of PEM by ‘Photoresstive voltage Uys —photovoltage between front and back sample surfaces Ver Yeg voltages evoked by the second order PEM elect in cases of short-circuited and open-citeuited fist ‘order PEM effect Yyru “open-circuit voltage evoked by the first order PEM effect Vioow View—PEM responses for plane-polarsed radiation with the electic vector in and normal to the plane of Incidence Viiow VESu components of the PEM response evoked by the ordinary diffusive PEM effect and electron PTME effect inthe case of investigations of the PEM eet of hot earrers208 M. Nowax, wna, Wn My-thicknesses of semiconductor and coating layers at front and back sample surfaces W— wil” "dimensionless thickness of sample WGS" wide gap se of graded energy zap structure Xs and bending Gi lye) nearby semiconductor surface 2 —eoeficent of proportionality between BPEM and PY responses, see Eg. (43) é festive quantum eficieny coeticent, sx Eqn (26) T —_“Shange in phase ofthe Beam on traversing the film of thicknes 2, see Eqn (2.24) ‘ty let constant ofthe investigated material, permitity of fie space < —Fermi enrey number of electon-hole pais generated by one photon 4-0, ange of incdenee of radiation upon sample 3 angle between B and n hg ma —componentsofreractive indices which describe absorption of radiation in @ semiconductor and in the tubstrate ofa sample sya —soefcients which describe the fundamental and other types of radiation absorption poss imaginary pats of semiconductor rlractive index for plane-polarsed radiation withthe electric vector Perpendicolar and parallel tothe external magnetic field B se _-—free carrier absorption component ofthe semiconductor refractive index for plane-polarised radiation with the electric vector perpendicular to the external magnetic Held B i —wavelength of radiation ‘Ai —bandwidth ofthe wavelengths of radiation incident upon a sample aig —so-illed cut-off valve of wavelength of radiation for which the PEM respons falls to half ofits value characteristic for rong absorption of radiation # relative magnetic permeability of the investigated material He ‘magnetic permeability of ree space ia —Booke magneton su Hs n-—difand Hall mobilities for electrons and holes Hoyt Huson iay-—mabilities of eletrons and holes moving along and normal tothe ¢ axis of hexagonal structure semiconductor iy —efletive photo-Hall mobility of earrers he —eetive mobility of earners, se Egn (6.14) : radiation frequency ? sitivity ofthe semiconductor material in a magnetic feld tre effective carrer fetimes deduced from the PEM (see Eqn, (220)) and PC (see Egn (3.21) investigations te so-called fatio lifetime of carers (se Eqn. (631) 2% lifetimes for electrons and holes 1” —time'of momentum relaxation of carvers “ha fn frtimes of energy relaxation due to eleciron-electron interaction, emission of optical phonons, and the ‘other mechanisms tthe efective relaxation time of carrier energy © phase diference between PEM and PC responses be ¥ss On @x-alfective changes in phase of the beam internally reflected from the front and back semiconductor Surfaces for plane-polarsed radiation with the clecitic vector in and normal . the plane of incidence a -yelotron frequency, see Eqn. (35) o ———plasma fequency, see Eqn. (34) o, ———frequency of longitudinal optic phonons SI units are used throughout this review 1, INTRODUCTION ‘There are several phenomena which are or may be called the photomagnetoelectric (PME) effects, in which the combined action of two external agents: light and magnetic field, give rise to specific electromotive forces in solids, eg. semiconductors, semimetals (see, e.g. Refs 79, 197, 302, 400, 578), some insulators (see, e.g. Refs 139, 342), or even organic materials (see, eg, Ref. 78), placed in a magnetic field and illuminated. This review is devoted to the PME phenomenon which causes an em4. parallel to the illuminated surface of a semiconductor, owing to the charge separation, by the magnetic fcld, of photogenerated carriers diffusing due to their different concentrations in various parts of a sample. This phenomenon is widely known as the photoelectromagnetic (PEM) effec. It depends strongly on wavelength, intensity and polarisation of radiation and magnetic field induction, as well as on the individual properties of the material investigated, and the configuration of the sample relative to the direction of applied magnetic field and opticalPhotoelectromagnetic efet in semiconductors 20 + @ [It : Sli ae lint in measurements ofthe ordinary frst order PEM eflect: a) trajectories of excess ‘carters which difuse in magnetic field due tothe gradient of their concentration inthe case of strong absorption ‘of radiation (ee Fig. 1.2} (b) measurement of the short-circuit PEM current, (c) measurement of the open-circuit voltage evoked by the PEM effect (broken curves represent the Mow of electric ‘current in sample of finite length. an. a, Fic, 12. Scheme of spatial distribution of excess carrier concentration in an illuminated semi- conduetor sampie (hw > 1,5, = 5) = 0 illumination. We shall begin with an elementary explanation of the simplest experimental case, the so- called first-order PEM effect. The Voigt geometry and experimental configuration used for ‘measurement of this effect are shown in Fig. 1.1. Photons of enerey somewhat greater than the energy gap of a semiconductor create free electrons and holes in it. In the case of strong, absorption of radiation in the investigated sample (K >> 1) the majority of all excess carriers are created near the front (illuminated) sample surface. When the recombination of carriers, is negligible at the sample surface, the electrons and holes diffuse into the bulk of the sample due to the excess carrier concentration gradient (Fig. .2). If magnetic field B is applied perpendicularly to that gradient, the diffusing electrons and holes are deflected in opposite directions in the third mutually perpendicular direction (Fig. .1). If the sample ends are connected externally in this direction the so-called short-circuit PEM current (Ipew) flows through the circuit (Fig. 1.1). In an open-circuited sample the carriers deflected by magnetic field build up a space charge, giving rise to a photovoltage. Although the so-called open- circuit PEM voltage (Vee) is limited by the conduction current through the sample (Fig. 1.1), in highly resistive semiconductors the electromotive forces evoked by the first order PEM210 M. Nowar, effect can be relatively strong. For example, in strongly illuminated CuO, placed in a magnetic field of B= 1.1T a PEM voltage of 20V was observed." In isotropic semiconductors placed in weak magnetic fields, both Ipru 88 Veew are proportional to the field induction and always change signs with the change of the sense of vector B. This PEM effect was discovered in 1934 by I. K. Kikoin and M. M. Noskov?°® in cuprous oxide, and its theoretical interpretation, based on the concept of the diffusion of optically created electron-hole pairs, was presented by J. Frenkel!!?” in the same year. However, it remained relatively uninvestigated for almost two decades. Then it was independently rediscovered by T. S. Moss and his coworkers?*°® and by P. Aigrain and H. Bulliard,?! 7” who also applied this effect to the measurements of bulk and surface recombination rates of excess carriers in semiconductors. These studies corresponded to the industrial development of semiconductors Itis worth mentioning that the name PEM effect was first used by E. Lifshitz.) but the ‘majority of papers in which it is used are a continuation of the papers by T. S. Moss.0%42°% ‘The name PEM is generally accepted for one type of infrared photon detectors which are based upon this effect (see chapter 7). However, in 36% of references quoted here, the simple general name of the PME effect is used for the presented phenomenon, as it was done first by J. Frenkel*”! On the other hand, authors of 39% of the references, especially papers in Russian, use the abbreviated name: photomagnetic effect (PME), which is rather unprecise, and is more appropriate for the effect of change of magnetic properties of some materials by illumination (see, eg, Ref. $59). Sometimes the PEM effect is also called the Kikoin-Noskov effect") or the photodiffusion current Hall effect.°***? G. Groetzinger and J. Aron®*** proposed calling the first order PEM effect the transversal PEM effect in ‘transversal magnetic fields in contrast with the longitudinal PEM effect in transversal magnetic fields. The latter phenomenon consists in a change of Dember photovoltage because of the presence of a transversal magnetic field; this is not discussed here. From the change of signs ‘of PEM responses with the change of direction of the magnetic field, the first order PEM effect is sometimes called the odd or linear PEM effect, but these names are not suitable because in anisotropic semiconductors the first order PEM response can also have a component which is a square function of B (sce chapter 4.1) Under certain experimental conditions—eg. if due to a fast recombination of carriers at the front surface of an optically thin sample (K < 1) some carriers low towards the illuminated surface and this component of current flow exceeds that away from the surface due to diffusion and recombination at the back surface--the PEM signal may be expected to reverse its sign. ‘This effect resulting from the drift of carriers to the front surface of a sample will be called hereafter the “negative” PEM effect. ‘The PEM effect has attracted considerable interest as a potential tool in investigations of many problems relating to the fundamental properties of semiconductors (see chapter 6) Therefore, it has been studied in many semiconducting materials (see Appendix 1), providing information about carrier recombination and transport, as well as about interaction of light with the investigated materials, Moreover, the PEM effect has attracted considerable interest sa basis for the development of photosensitive devices (see chapter 7) ‘Owing to its physical nature, illustrating well mechanisms of phenomena which occur in semiconductors, the PEM effect is discussed in many textbooks on semiconductor phys- ies,2®614" as well as in monographs on photoelectri!®$92122-996297.486.550 and galvano- magnetic™” effects. Moreover, the PEM effect is presented in monographs on experimental methods of semiconductor investigation! "2479-57 and in monographs on photon detectors.°192°+6*+*) Unfortunately, because of the complexity of the PEM effect, and the fact that this effect is only one of a great number of phenomena discussed in those books. information presented there about the PEM effect itself is rather scanty and simplified. In 1956 O. Garreta and J. Grosvalet'*®” published the first review on the PEM effect, and inPhotoelecromagnetc effect in semiconductors au 1968 Yu. I. Ravich'*”" published a monograph (in Russian), which presented results of a PEM investigation carried out up to 1965. However, during the last twenty years the investigations have been intensively continued all over the world. The theory of the PEM effect was extended, new experimental data were obtained, new methods of using PEM investigation for determining semiconductor parameters were worked out, the construction of PEM detectors of infrared radiation was improved. Short discussions of some special cases of PEM effects were presented in 1978 in a review paper by I. K. Kikoin and S. D. Lazarev?®?! and in a popular paper by the latter author. The present monograph summarises results of the investigation on the PEM effect in semiconductors, which have been performed all over the world during the last 51 years, with our comments on them. Over 67% of the references were published after 1965 and 27% was published after 1977. In addition to the ordinary PEM effect there are several associated effects, eg. the impurity PEM effect (see chapter 3.1.1), the second order PEM effect (chapter 3.2.1), optically induced thermomagnetoelectric effects (chapter 5}, which are briefly reviewed here. However, the phenomena which need additional physical agents in comparison with the PEM effect, e., the acoustophotomagnetoclectric effect"** are not presented. Owing to the limited volume of this paper, also many of photoelectric, magnetoelectric, thermoelectric, photothermal, photomagnetothermal and thermomagnetoelectric effects which coexist with the PEM effect could not be presented. Fortunately, some results caused by those effects (evoked by only one external agent, eg. radiation or magnetic field) can be separated from the PEM results (see chapter 6). The magneto-induced photovoltaic effect occurring in piezoelectric semiconductors (see, eg, Ref. 231) is also not reviewed here. 2, GENERAL FORMULATION ‘The theory of the PEM effect develops in two distinct directions. On the one hand it is based on the solution of a transport equation, the so-called Boltzmann equation, which involves the dependence of carrier relaxation time on energy.'!®-S°° On the other hand the theory based on the phenomenological equations is developed and it assumes that the effective mobilities of electrons and holes in a semiconductor placed in a magnetic field are known, In the latter approach special attention is given to the optical aspect of the problem as, for example, to the dependence of the PEM effect on the wavelength of the incident radiation. Because the Lorentz force is dependent on the microscopic velocities of carriers, the frst description of the PEM effect is more correct, However, the basic difficulties in this description: the necessity of taking into account the real dependence of the eflective relaxation time of carriers on their energy, and the spatial inhomogenities of carrier concentration and current densities, rather complicate this theory. Therefore the latter theory is usually applied in PEM investigations. 2. Basic Equations of the Phenomenological Theory of the PEM Effect ‘The phenomenological theory is based upon the solution of Maxwell's equations, Poisson equation, the continuity equations and the transport equations. The solution can be obtained analytically only for special cases. To simplify the consideration one assumes that: (a) a homogencous semiconductor is placed in a uniform, steady magnetic field; (b) the magnetic field is so weak that in equations on p(B), the terms with second and higher orders of B are negligible; (c) all parts of the semiconductor have the same temperature and the carriers are described by the Boltzmann statistics. The neutrality aspects are not specifically invoked in the theory which follows. They were discussed in Refs 542 and $44. The aforementioned assumptions are justified in most of the experiments on PEM effect. Certain exceptions will be discussed in detail in the chapters to follow.a2 M. Nowa. In the present case, transport through a semiconductor in the presence of a static electric field E and steady magnetic field B, under bulk photogeneration is described by the following equations 1 = enn + eD, gradn, — pT, xB] eu 1, = eng — eDygrad my, + sylIyx BY 22 khan, es Liv, 24) In these equations, phenomenological distinction is made between Hail and drift mobilities, scattering models not being considered. In the case of degenerate energy bands in the investigated semiconductor, the same equations still apply; however, the Hall and drift mobilities as well as diffusion coefficients for holes are certain weighted averages, as were used, e.,, in Refs 387, 450, 474 and 542. It is worth mentioning that relatively few fast holes can make a large contribution to the PEM current or voltage. In the case of interband (intrinsic) photoexcitation of electrons and holes, the following simplification applies Bel (25) where kee ton (2.6) Kept Ky, (27) kna~' = Azxn(ia)-* (28) a? = 0,5(n? — x? — m3 sin? 8) + [0.25(n? — x? — nj sin? OP + nx?) 29) Coefficients x and f take into account the fact that radiation is absorbed in semiconductors ‘owing to various absorption mechanisms, e.g, fundamental and free carrier absorption. All these mechanisms affect the spatial distribution of radiation in a sample as well as the ratio of carrier photogeneration. The k, is the effective absorption coefficient of radiation which describes the attenuation of radiation intensity in the direction normal to the front sample surface. Since the reduction in amplitude of a plane wave in an absorbing medium depends directly on the distance travelled in the medium, the loci of points of equal amplitude are planes parallel to the surface of separation, as shown in Fig. 2.1, and the value of the coefficient k, depends on the angle of incidence of radiation into the sample (see Eqn. (2.8). The radiation intensity I in a sample is a cumbersome function of the sample shape, dimensions, and the optical parameters of polarisation and angle of incidence of radiation Figure 2.2 shows the spatial distributions of radiation intensity in semiconductor samples of different thicknesses. They were calculated using the more general, and convenient for the PEM investigation, formula for 1, which was given in Ref. 433 for the case of non-normalPhotoclecttomagnetic eect in semiconductors a3 Fig. 612. Dependence ofthe PEM response on the position of He-Ne laser beam atthe surface ‘of pSi covered with mechanically scratched and undescut in CP-4 fm of SiO, (, = 120nm). 0 2 60 40 Ui) 20 Fic. 613, Dependence of PV(l) and PEM(2) responses on the position of a He-Ne laser beam along p-Si sample covered with mechanically serached film of SiO: (3) total signal of PEM and PV eflects(w, = 120 devices, because the measurement methods used are based on theories assuming only homogeneous samples, The more advanced PEM methods of determining parameters of inhomogeneous semiconductors are given in the following paragraphs. It must be emphasised that not only the local values of surface recombination velocity but also the reflection coefficient influence the PEM response (see Figs 6.12 and 6.13). Investigation of the PEM effect is more sensitive to the inhomogeneity of a semiconductor surface than the investigation of photovoltaic effect (Fig. 6.13). 69.1. Methods using bulk PEM effect investigation. Sikorski'*® pointed out that the relation (42) between the bulk PEM voltage and the photoelectric one is a measure of the sum of carrier mobilities for the illuminated area, and can be used as a method of investigation of inhomogeneous semiconductors. Measurements of a may enable, by simultaneous measure- ‘ment of normal Hall voltage, the Hall mobility of minority carriers to be determined, as was done, eg. in Refs 506, 368, 369 and 508.a M, Nowax, Mobitities can be obtained from integrated measurements referring to large illuminated areas as well as from point measurements made by illuminating very small areas.**3°? When illuminating the whole sample (current and voltage contacts masked) the results obtained will allow the calculation of an average mobility for the whole illuminated area, On the other hand, the point measurement gives a local value of the carrier mobility. It is possible {o apply point measurements and to plot 2 map of the mobility distribution of the sample taking into account the mobility and resistivity changes appearing over small areas:°° The obtained results are in agreement with those obtained by a small moving light spot method.!?°°) Markowska®” presented a detailed analysis of the usability of this method in semicon- ductor investigations, as well as the uncertainty of the estimated values of carrier mobility. She found out that the presented method of measuring mobility is applicable to semiconductor ‘materials such as Ge and Si, if the bulk photovoltaic eflect is evoked by at least a 2% specific resistivity change across the carrier diffusion length. In contrast, the photovoltaic effect is too small and the precise measurement of the bulk PEM voltage gives rise to great difficulties. The bulk PEM voltage is from $ to 20 times smaller than the bulk photovoltaic voltage evoking it. Therefore, the accuracy of the mobility measurement depends on the accuracy of the bulk PEM voltage. Although the above-presented method is applicable in principle to semiconductors in which the resistivity change in one chosen direction is much greater than in the remaining directions, 2 series of tests showed that the direction of the specific resistivity change can be arbitrary. However, the measurements of the bulk PEM and PV voltages must be performed twice in different directions, measuring the photoelectric voltages between various electrodes with and without a magnetic field. For the measuring accuracy of the bulk PEM voltages, the ratio of PY voltages along mutually perpendicular directions must be higher than 2 or less than 0.5. ‘The measurements of short-circuit currents evoked by the bulk PEM and PV effects are less suitable for measuring carrier mobility in inhomogeneous semiconductors than the ‘measurements of open-circuit voltages. This is due to the strong influence of the sample resistivity inhomogeneity, and magnetoresistance on the values of the measured cur- Tents 268269) 6.9.2. PEM investigations of graded energy gap semiconductors. it was shown in chapter 4.4 that the PEM response in graded energy gap semiconductors is very sensitive to the parameters of the investigated structure. Therefore, in many laboratories attempts were made to work ‘out PEM methods of investigating graded gap semiconducting materials. Unfortunately, due to the complexity of the examined phenomenon (see chapter 4.4) the performed measurements were very dificult to interpret. Very rough approximations were made. Cohen-Solal et al!!!'9# determined the lifetime and mobility of carriers in graded-gap Cd,Hg, ,Te structures. In a theoretical description of the measurement methods, the so- called ideal and pseudo-homogeneous graded-gap structures were considered. In the ideat structure all parameters are constant except the energy gap E, which changes with the distance from semiconductor surface. The physical significance of the pseudo-homogencous structure is that the net movement of excess carriers is a diffusionable one, characterised by diffusion length varying with distance from the structure surface. The linear variation of L was taken into account. Cohen-Solal er al*!'-*¢” assumed in addition the photogeneration of carriers only in those places of the graded-gap structure where E, = hv. ‘The carrier mobility in graded-gap semiconductors was determined"! from the magnetic, field dependence of PEM effect using a method very similar to the Kurnick~Zitter one (see chapter 6.3.1). This results from the theory given by Cohen-Sotal and Marfaing!"?” that for a pseudo-homogeneous graded gap structure the value of (Bi/lpey)? is proportional to B, whereas for the ideal graded-gap structure B/Ipew is linear with B*. In both cases the factor of proportionality divided by the intercept of the straight line at zero magnetic field is equal to the square of some effective carrier mobility, which was interpreted as the value of localPhotoclectromagnetc effect in semiconductors 35 mobility of carriers in the place of their photo-generation. However, it was experimentally observed that the effective mobility estimated in this way for photons of energy hy was always higher than the actual electron mobility in homogeneous Cd,Hg, - ,Te of band gap E, = hv.*1?” This was explained by the drift of excess carriers into the part of the graded-gap structure with a smaller energy gap. The Kurnick-Zitter method (see chapter 6.3.1) was used directly for estimating carrier mobility in graded-gap GaAs, -..,Sb,P,."\4°! However, it is rather hard to explain the physical meaning of the obtained results, ‘The values of carrier lifetime in graded-gap Cd,Hg, ..Te were estimated from the ratio of, PEM to PC responses, and were interpreted as the local value characteristic for the place of semiconductor structure in which energy gap is equal to the photon energy." By changing the energy of photons incident upon a sample, the spatial distribution of carrier lifetime in the graded-gap material was estimated. In Ref. 140 the surface recombination velocity of cartiers in GaAs, .. ,Sb,P, was estimated using the method based upon the change of sign of PEM signal with changing wavelength ‘of radiation which illuminates the semiconductor (see chapter 6.2.3). This method of investigation was proposed by Chattopadhyaya and Mathur.1°” The theoretical assumptions which are the basic principle of these investigation methods make the obtained results very unreliable. [t seems that the magnetic field dependence as well as the spectral dependence of the PEM effect in graded energy gap semiconductors should be fitted with much more realistic models. The theoretical description will be very complicated and in order to obtain quantitative information from the PEM measurements, the knowledge about some important parameters of the investigated material will be necessary. Therefore, the investigation of graded-gap materials should be more complex. 693. PEM methods of investigation of semiconductor layers with anomalously high photo- voltages. Adirovich et al!" used spectral measurements of the PEM effect to determine some parameters of CdTe films with anomalously high photovoltages. The measurements were performed in two series, for illuminations of front and back (through the substrate) surfaces of a film. When strongly absorbed radiation was used, the PEM response was much greater for front surface illumination than for illumination of the back interface between the film and its substrate, In experiments with weakly absorbed radiation, the positive and negative PEM responses were measured for front and back surface illumination, respectively. Hence, it was deduced that the carriers recombine much faster at the surface which adjoins the film substrate than atthe rontone(s, « 53). Besides, Adirovicher al!!*¥assumed that W= w/L S Sz = s.w/D. [it simplifies the analysis of the experimental results because formulae derived for these specific experimental conditions may be used. For K» 1, K > W, K > S; and W> Sy, (4.12) reduces to'*?” Ire = ~ 31, Bel Lily (6.42) Assuming fi = 1, this formula can be used for determining the value of uel. For K < W, K > 1, S > W> S,, the extremum negative PEM signal observable for back sample illumination should be" eBlvlgl? eB en = (643) Combining (642) and (6.43) the values of effective mobility 4, and diffusion length L of carriers can be obtained. Performing investigations on CaTe thin-films with anomalously high photovoltages, it wasa6 M. Nowa found that the value of effective carrier mobility estimated using the presented PEM method was equal to the value obtained from the photo-Hall measurements."*" However, itis worth mentioning that the value of such a parameter is strongly dependent on the radiation intensity. ‘The value of carrier lifetime determined from the PEM measurements was about four orders, of magnitude lower than the time constant estimated from the decay of the photovoltaic effect after a sudden blackout of the sample!!! This was interpreted as being the result of carrier trapping in the investigated material In Refs 14-16 and 18 the number N of p-n junctions in series in CdTe thin-films was estimated from the measurement of the saturated (for high illumination intensity) value of PEM voltage using the following formula'*”*! 2koT (6.44) Knowing the absorption coefficient k, of radiation for which the PEM response changes from negative to positive with decreasing radiation wavelength, knowing the values of L and D, and assuming S, < W, the following relationship'"5! may be used for determining 53, as was done, eg, in Ref. 15, W+ kw Sree esha) (645) 69.4, PEM methods for determining parameters of semiconductors with metallic inclusions. Assuming (a) a thick sample (W > 1) of n-InSb-NiSb with one-dimensional microinclusions which have conductivity o, = dje(sen. + Hy); (D) influence of magnetic field only on the motion of carriers in the InSb matrix; (C) He = bie 2 My = Hays Te = &ei (d) surface photogeneration of carriers; (e) small illumination of a sample; and (f) negligibility of surface and edge effects, then the ratio of PEM currents evoked in samples oriented perpendicular and parallel to the NiSb needles (see Figs 4.12c and a) are given by!"”*) (6.46) Zhadko et al‘*79 used this relationship for experimental determination of 5, Under the same, above-presented conditions the ratio of currents evoked by transverse photodiffusion and PEM effects in n-InSb-NiSb samples is given by'*"* siny cosy (sie +5 5 ii where y represents the angle between NiSb needles and the sample surface. Zhadko et al‘*?*! used (6.47) to determine 5, for samples with y = 45°. Gulyi et al'!® checked that (6.47) reduced for u.5,sin?y > i, describes very well in @ qualitative way the experimental dependence of Irp/Irem on the value of ¥. ‘The parameters of the InSb-NiSb structure can also be determined by fitting the magnetic (647)Photoelectromagnetc effect in semiconductors Sy =syweb? = syweyb? Sp = syweL-? = syyweyl-? fehl + reFfye™® — IrvFiye"Keos (vy + oy — 1)" r= 7) = drawl" iv = rly + rivtdvilvely + 2rivravtaviverv eos (Bay + Bay ~ 31 ~ viv — @2v) Th = ry + rivdvtivedy + 2rsvravtavisvesv008 Bay + Bay + Pay ~ 53 — av) T= thvthvety sindy = —Eravsin pay + ravtaviavery sin (Bay + Bay ~ 6: — yw)lFit cosy = —[ravc08 Gay + Fivtavizvery cos Bay + Bay ~ 51 — rivlFiv sin oy = [ray sin @sy + ravtsvEavesy sin Bay + Bay + Pay — 5s — 7a)! 608 py = [ray COS Pay + ravtsvitavesy C05 (Bay + Bay + Pay — 53 — yavi)rv" ew = UL + iris ay + 2revras iv 008(@iv + Bus yy — 6)? sin@,=nonr*sinBo, — 6,= wincos6, sin yoy = FevFa+ ryverv SiN (Pev + Pur vw — 4) Cos riy = [1 + rarer C0S(Oiv + Qusny ~ Ale r= [ay — a)? + (b-1 — BYP Id * sings = 2a, saXrsd)~* 608 is = (a? + BF — a? — bEXrad,)~! th= 4a}, +b} yd! sin Bes = a,b; — by saXtisdd~* 608 Bix = ahs + Bx + a4a,-1 + bid sNtad)™* 20 (2.22) (2.23) (2.24) (2.254) (2.25) (2.26) (2.27a) (2.27) (2.28a) (2.28b) (2.29) 2.30) (231a) (2316) (2.32) (233a) (2.336) (234) (235a) (2.356) (236)218 M. Nowak sin Bis = (aiby — 44 sbdieL 2a? + b3I"* (237a) cos Bis = (a? + b? + axa, yNisL2a? + b7))* (2.376) rie = {[ln?_y ~ x2 )ay — (rn? — x?)a,— + [binds + by yn? — 2a, fb, + bP ST? (2.38) sin @ye = 2[ba,-.n?_ (a? + ? — n§sin? 6) b,-sayntla?, + b24 ~ nisin? Ore f)* (2.398) 608 gap = Link + xP-1)*a? + Bf) — (on? + wPMCa2 4 + B7-s)Mrnf)* (2.396) ip = Mah + BR MnP + xP Kn? + PVT (2.40) lel baa ee fe ae (241b) (2.42) =a sin Bie laren ate) (2.43a) he oo. lao e _ 4 = (aya4 + a)? + 0j-1 + BY (2.44) Si= Cer — sda, + (0? — xP), + (banks + jan? + 2a,-sa(b, + 6,-0))? (2.45) 4a 0K — MAD + MIN AM 4 — B20) (2.46) Th = mam ia. + Baw M4 MID; 1K ean a2 = 0.5(n} — x? — n§ sin?) + (0251? — x? — nB sin? Oy)? + nPx?]"? (248) b= near! (2.49) i = 1,2,3 represents the following interfaces in the investigated semiconductor structure, see Fig. 23. The index V must be replaced by indices P or $ for plane-polarised radiation with the electric vector in and normal to the plane of incidence. Expressions (2.16a) and (2.16b) are the general solution for Tpex. The first terms in these relationships describe the case of negligible internal reflection of light in the semiconductor. The sccond terms describe the short-circuit current originated by the interference PEMPhotoelectromagnetc eflet in semicondactors 219 cffect,“223 the additional PEM mechanism evoked by the inhomogeneous distribution of radiation due to the interference of radiation internally reflected from the sample surfaces (Fig. 2.2). The analogue expressions for Vor can be easily obtained from the Thevenin theorem (2.15), Using (2.1), (2.2), (210), and the above-assumed conditions, the transverse magnetoresistivity of the semiconductor can be found!” age_Hatangel? p fein FA) Ce + Ba Oe ee RDS «QWs, #5) —R ame" QWs, —s3e-™™} (2.50) It is interesting that (2.50) describes the results of room temperature magnetoresistance investigation on InSb better than formulae derived from more sophisticated theories.'*°5-55° However, it is recommended to use for p = p(B) the experimental data rather than those resulting from that simplified theory. Expressions obtained from (2.16) for normal incidence of radiation (@ = 0°) on a single semiconductor wafer (r,y = 0, fyy = 1), in which the internal radiation reflection is negligible (ry = 0), after putting into them the following approximations, are identical (except for differences in notation) to those derived in the well-known theories of the PEM effect given Dy Lile!?*" (1. = ites Hn = Hn), Amnith* (age + Hyn)B <« 1), Gartner!**” (die + tiun)B < 1, Kruse!) (, ites Hn = Huns Te = Tas K > 1), Kurnick and Zitter'*?* and Lagrenau- die and Pires de Carvalho!??” (4. = pistes Hy = Kitts Te = Ty» K >> 1, W > 1), Van Roosbroeck'**?) (ine + Hsn)B-< 1, K > 1), From (2.16) the formula reported in the previous papers of the author'*?0-422,42.424.427.432) can also be obtained. It should be noticed that for r,y = ry = 0, Ty = 1, 8 = 0°, (ite + Hrn)B « 1, (2.16a) is identical to the formula derived by Schetzina'*?®” for PEM current in relaxation semiconductors. In such materials, e.g in high-resistivity crystalline or amorphous semiconductors, the dielectric relaxation time is much greater than cartier lifetimes and the bulk charge neutrality is over-all controlled by rapid recombinatio whereas in the so-called lifetime semiconductors (with carrier lifetime greater than dielectric relaxation time) the charge neutrality is maintained at equilibrium through fast dielectric relaxation processes. The formal identity of the descriptions of PEM effects in recombination and relaxation semiconductors was first noticed by D. C. Look,'*** and was used for instance in Ref. 8. Assuming ryy = ray =0, iy = 1, 0 and taking into account multiple radiation reflection within the sample but neglecting the interference effect (e.g, for the case of nonmonochromatic illumination of the sample AA > 12(2nw)~'), (2.16) can be reduced into the formula given by Genzow et al.‘'6° Using the results of Merz et al.7" it is obvious that in this case the values of all trigonometrical functions in (2.16) should equal zero and Iy should be replaced by a fe Aye]! ten [eats Ave a] 2s) The general formulae for Icy and Vey arc rather cumbersome functions and can be effectively used only for describing PEM experiments involving computer methods of data Processing, as was done, e.g, in Refs 44, 420. Some much simpler formulae, which apply to special experimental conditions, are given in chapter 6. While using them it should be taken into serious consideration that omitting even one of the semiconductor parameters can cause not only a quantitative but also a qualitative change of the theoretically deduced PEM signals, Kang and Cristoloveanu*® proved that even for very thick GaAs samples (K = 1400,20 M. Nowak W = 175) with high recombination velocity on the front surface, some simplifications, eg, the hypothesis of surface photogeneration of carries or the hypothesis of negligible concentration of excess carriers at the back sample surface, can be responsible for misleading conclusions drawn from PEM investigations. Moreover, there is a qualitative restriction: the PEM effect theory which assumes surface photogeneration of carriers cannot describe the negative PEM effect. It is also evident that the optical properties of semiconductor surface coatings, ¢ oxide films, must be included in the description of some PEM experiments, as was done in 216). Formulae (2.16) describe correctly the experimental dependence of PEM effect on wavelength and absorption coefficient of radiation (chapter 3.1), arbitrary (except of quantising) magnetic field (chapter 32), angle of incidence and polarisation of radiation (chapter 33), values of recombination parameters and concentration of carriers in the investigated semiconductor (chapter 34), and on its thickness (chapter 3.7). The general formulae are especially useful in PEM investigations on thin-film semiconductor samples, eg, on 1.5 um thick films of n-GaAs ‘or on the layer-semiconductor GaSe, when the internal radiation reflection occurs. These formulae are also very useful for optimisation of PEM detectors (chapter 7). They allow the ‘working out of new methods of measuring semiconductor structure parameters (See, €2. chapter 64) and the definition of the correct ranges of application of the other PEM methods of semiconductor investigation (chapter 6). Evidently, despite their generality, 2.16) cannot describe all complicated problems of the existence of the PEM effects in real semiconductors, ‘eg. in anisotropic, inhomogeneous, or graded energy gap semiconductors (see chapter 4). However, i is @ good basis for the analysis of more complicated PEM effects. 3. DEPENDENCE OF THE PEM EFFECT IN AN ISOTROPIC, HOMOGENEOUS SEMICONDUCTOR ON EXPERIMENTAL VARIABLES 3.1, Spectral Dependence of the PEM Effect Due to the relatively strong dependence of the optical parameters of a semiconductor on the wavelength of radiation, the change of this experimental variable radically influences conditions in which the PEM effect occurs. To simplify the analysis of this phenomenon one can take into consideration, as a first approximation, the case of negligible internal reflection of radiation from sample surfaces (ry = 0 or K > 1). Then for s, <2, the lrex increases and saturates with increasing absorption of radiation (Fig, 3.1). The saturation takes place for {greater values of K with increasing W. The spectral dependence of the PEM effect is weaker for 5; <3. The PEM response drops considerably at the absorption edge when carriers are ‘optically excited throughout the whole volume of a sample instead of only at its surface. Decreasing the value of K for the case of s, > s3, the excess carrier concentration near the front sample surface becomes much smaller than in the sample bulk. So the carriers diffuse from the bulk to the front sample surface and the negative PEM effect occurs. The signs of Trew and Vee ate opposite to that of the normal PEM effect occurring for strong absorption ‘ofradiation and negligible recombination of the carriers at the front sample surface. Decreasing, W or increasing the ratio s/s, the negative PEM effect can be observed for greater values of K (see Fig. 31). It can be even stronger than the normal PEM effect evoked in the same sample but with strongly absorbed radiation. However, the greatest value of Ipey can be observed for the normal PEM effect in a sample with a negligible value of s, and great value of s,. It should be underlined that all features of spectral characteristics shown in Fig. 3.1, which were first theoretically described by Gartner,"*” have been observed in experiments, see, eg, Ref. 88 and Fig 62. The transition from negative to normal PEM effect with decreasing wavelength of radiation illuminating a semiconductor was also reported in Refs 205, 206, 351, 448-450, 584. However, for wide energy gap semiconductors, eg. for Si(17*8®) illuminated with strongly absorbed radiation, some fall-off in the PEM response was observed ‘with the decreasing of radiation wavelength. This disagreement between the presented spectralPhotoelectromagnetic effect in semiconductors a Fic. 31. PEM shortcreuit current vs the product of absorption coefficient and semiconduct ‘highness for diferent values of carier lifetime and surface recombination velocities (n/t, = 10° Blt = 28. jl ay = 25. te = fe =O" Ue + syn 14 ry = Othe dashed curves Fepreseat the negative PEM effect 6 = — jew) ¥ curve marks from the table below. Chev ae Nese aa oar aren oreo noe eee sii, Wana i ef 758 2 Alum) Fic, 32. PEM open-circuit field in InSb vs photon energy for diffrent semple thicknesses and surface recombination velocities, assuming M() and n() aftr Seraphin and Bennett?" The dashed ‘curves represent the case of negligible intern 1 sig = 006mm3/Vs, L = 133 pm, my = Hoy = 18, B= Ty wy — mye 8 = 10°LepBldane + bdB (yw = 05m, 5, = Liss = HOF m/s (eale x 10, (2)03 ym, Tims, Lams (8) 24m. mm/s ‘characteristics and experimental results has been explained by means of the PEM effect theory suitable for semiconductors with a surface space-charge layer (see chapter 42). The interference of radiation internally reflected in a thin semiconductor sample can strongly influence the distribution of radiation over the sample thickness (see Fig. 2.2). The steady light wave which exists in such conditions produces an additional PEM mechanism, the so-called interference PEM effect." In this case the radiation wavelength is important for the PEM effect, not only due to its influence on values of optical parameters of a semiconductor, but also due to its direct influence on the spatial distribution of the steady light wave in a sample. The oscillatory dependence on photon energy is specific for the interference PEM effect (Fig. 3.2), similarly to the case of interference PC observed, eg, in InSe and GaSe!****°" The period of these spectral oscillations depends on n and decreases