Localised states and their capture characteristics in amorphous phase-change materials
Localised states and their capture characteristics in amorphous phase-change materials
0 & Martin salinga
As phase-change materials are poised to play a key role in next-generation computing systems, improving the current understanding of electrical transport in their amorphous phase can further strengthen their technological competitiveness. even though the interaction of charge carriers with disorder-induced localised states largely affect the field-dependent conductivity, a clear link between electrical transport and specific features of the electronic density of states (DOS) could not be established yet due to a lack of knowledge of the capture characteristics of trap states. Here, we address this knowledge gap and employ modulated photocurrent spectroscopy (MPC) to investigate localised states in the frequently studied amorphous phase of Ge2sb 2t e5. Additionally, we present results on the Dos in the bandgap of amorphous AgIn-doped sb 2t e, which has not been subject to highresolution DOS spectroscopy before. We find experimental evidence for clearly non-constant capture coefficients among a continuous spectrum of localised states in both studied materials. According to this observation especially in AgIn-doped sb 2t e, where no pronounced defect can be detected as main channel for carrier emission, we point out the necessity of modifying the current poole-Frenkel-based transport modelling.
charge carriers17?21. However, the Ielmini-Zhang-model of charge carriers hopping with a constant travelling
distance between neighbouring states is incompatible with the well-known band transport concept11. Le Gallo et
al.22 addressed this shortcoming by proposing a PF-based transport model that describes field-dependent
conductivity in amorphous Ge2Sb2Te5 and GeTe remarkably well without assuming immediate re-trapping of emitted
carriers. Nonetheless, PF-based transport modelling so far only includes trap states attributed to a single energy
level, which is commonly attributed to a structural defect at a specific energetic distance to the band edge16,22?24.
This approach appears plausible at least for PCM containing germanium such as amorphous GeTe, where
underor over-coordinated Ge-atoms have been associated with electronic defect states in the bandgap25?27. However,
in germanium-free PCM, which might lack an appropriate defect as main channel for PF assisted charge carrier
emission, the applicability of current PF-based transport modelling is questionable. This presumption is
strengthened by the fact that previous PF-based transport modelling on amorphous Ag4In3Sb67Te26 yields an
unreasonably large intertrap distance12.
Recently, Kaes and Salinga made clear by linking subthreshold electrical transport and the density of
electronic states (DOS) that more precise knowledge on the density of localised states, but also on capture
characteristics of such states is needed to better understand electrical transport in amorphous PCM24. The capture
characteristic of a localised state with respect to a certain type of charge carrier is typically expressed by the
capture coefficient c= ? ? ?th as product of thermal velocity ?th and capture cross section ?28,29. As such, c measures
the efficacy of a localised state for capturing a charge carrier. In p-type conductivity materials such as amorphous
PCM30, the capture coefficient for holes cp is of predominant importance for electrical transport.
A key technique to obtain experimental input on both density and capture coefficient of localised states in
the bandgap of amorphous materials is modulated photocurrent spectroscopy (abbreviated MPC, sometimes
also referred to as IMPS for intensity-modulated photocurrent spectroscopy). Decisively shaped by works of
Br?ggemann, Longeaud and others29,31, MPC spectroscopy has been used for numerous investigations of the DOS
in a large variety of different materials, from amorphous silicon to lead sulfide quantum dot arrays32?36. Other
methods to examine the electronic structure of amorphous PCM films such as x-ray or ultraviolet photoemission
spectroscopy typically do not offer a sufficient energy resolution to observe distinct features of the bandgap37?39.
The working principle of MPC spectroscopy is based on intensity-modulated illumination with photons, which
generates free charge carriers in the material leading to a modulated photocurrent. During the experiment, the
photocurrent amplitude and phase shift with regard to the sinusoidally modulated illumination are recorded as
function of modulation frequency. These experimental data can be linked to the density of localised states by
interpreting the measured amplitude and phase shift in terms of free charge carriers that are trapped by localised
states and released back to the band after some delay. In particular, it has been commonly agreed upon that the
phase shift between excitation and modulated photocurrent predominantly originates from the thermal emission
of trapped charge carriers (e.g.31,40,41). In this picture, photons are solely generating free charge carriers, they are
not expected to contribute to the measured MPC signal in any other way, e.g. via optically induced transitions
involving localised states.
So far, MPC spectroscopy was used in studies by Longeaud et al.42 and Luckas et al.43,44 to gain remarkable
insight into the DOS of amorphous GeTe and Ge2Sb2Te5. According to their MPC studies, the bandgap of these
PCM exhibits Gaussian-shaped peaks of localised states related to structural defects. In addition to these
pronounced peaks, disorder-induced spectra of localised states were found with exponentially increasing density
towards both band edges. Especially with respect to these spectra of localised states, up to now the analysis of
MPC results has been performed under the restrictive assumption that the investigated states exhibit one
common capture coefficient (cp = const.)42?44. This simplification makes it much easier to analytically link
experimental MPC data to the DOS, since cp may then be assumed to be independent of energy29.
In the present work, we challenge this assumption of a constant capture coefficient based on precise
experimental input for the density and capture characteristics of localised states. We suggest crucial improvements
to the already established method of MPC spectroscopy, including both experimental and analysis-related
aspects. Our study focuses on high-quality MPC measurement of two materials. Amorphous Ge2Sb2Te5
represents the probably most popular and widely studied PCRAM material45. By additionally choosing amorphous
AgIn-doped Sb2Te (more precisely Ag4In3Sb67Te26), we provide very first insights into the DOS in the bandgap of
this germanium-free PCM that stands out due to its drift characteristics, a property relevant for storing multiple
levels in a single PCRAM element46,47.
MPC spectroscopy measurements. Figure?1 presents the obtained MPC spectroscopy measurements on
amorphous Ge2Sb2Te5 and Ag4In3Sb67Te26. Due to the experimentally demonstrated p-type conductivity of
amorphous PCM30, the MPC signal is most likely dominated by trap and release processes of holes29,42. These holes
interact with localised states within the bandgap at energy levels below the Fermi level, which is located in the
lower half of the bandgap near the bandgap center. Contributions to the MPC signal from electrons interacting
with localised states above the Fermi level can be neglected. This implies that only localised states below the Fermi
level can be probed by MPC spectroscopy. Apart from this, it is a common constraint in MPC analysis that exact
values for quantities such as the DOS at the band edge N(E V) = NE V or the extended-state mobility ?ext,p are not
known. Consequently, instead of plotting the pure DOS N as function of probed energy E?p, usually a so-called
MPC DOS being proportional to N is plotted against energy (see methods).
Looking at Fig.?1, it can be seen that a coherent DOS is composed of locally overlapping MPC scans, which are
recorded at different temperatures. Each MPC scan originates from measuring amplitude and phase shift of the
photocurrent while sweeping through the modulation frequency. During this process, the modulation frequency
determines at which energy level localised states are probed. More precisely, using a higher modulation frequency
implies that localised states at an energy level closer to the valence band edge are probed. Eventually, the essential
limited by recombination zone
of localised states
(?V = 27.3?0.8 meV)
to MPC signal
curved MPC scans
[E?p-EV](T = 0 K) in eV
limited by recombination zone
of localised states
(?V = 35.9?0.7 meV)
probing energy levels
near Fermi level
[E?p-EV](T = 0 K) in eV
analysis step is to find the correct capture coefficient for holes cp of the probed localised states, because only then
the aggregation of individual MPC scans yields a coherent DOS. Considering that cp itself depends on
temperature T as in cp(T) = kc ? T1/2 due to the thermal velocity of charge carriers29, we suggest to introduce the factor kc.
Thereby, the productkcNE V can be used as temperature-independent tuning parameter for the matching process
of MPC scans (see methods).
During this process of determining the capture characteristics of localised states, it is crucial to consider that
charge carriers trapped at energy levels closer to the bandgap center (and thus measured at lower modulation
frequencies) have an increasing probability of recombining instead of being re-emitted to the band. Since the MPC
analysis employed in the present work can only handle an MPC signal dominated by trap- and release processes,
segments of MPC scans corresponding to energy levels dominated by recombination traffic must not be used to
form a coherent MPC DOS and are therefore excluded from further analysis (marked as thin lines in Fig.?1). For
identifying which segments must be excluded, we employ an experimental procedure in which MPC scans for a
specific temperature are recorded at various light fluxes (see methods).
At first sight, for both materials MPC scans seem to form a somewhat coherent MPC DOS as constant capture
characteristics (kcNE V = 5 ? 1013 s?1 K?1/2 eV?1) are assumed for the probed localised states in the bandgap
(Fig.?1). A continuous spectrum of localised states is observed, for which the MPC DOS appears to decrease
exponentially from the valence band edge towards the bandgap center. Local exponential fits reveal slopes (also
called decay energies ?V) of 27.3 ? 0.8 meV (Ge2Sb2Te5) and 35.9 ? 0.7 meV (Ag4In3Sb67Te26) close to values
previously found in MPC spectroscopy studies on amorphous PCM24,42.
As Ag4In3Sb67Te26 has a higher conductivity compared to Ge2Sb2Te5, it is possible to measure MPC scans with
satisfactory signal-to-noise ratio for Ag4In3Sb67Te26 down to 90 K, while low-temperature data on Ge2Sb2Te5 are
limited to 120 K. With regard to our results for Ge2Sb2Te5, MPC scans recorded at temperatures around 200 K
and corresponding to energy levels closer to the bandgap center seem to be separated from the continuous
spectrum of localised states. These separated MPC scans are characterised by poorer overlap and a slight, but explicit
curvature. This observation fits with studies by Luckas et al.43,44,48, revealing that a pronounced peak of localised
states could be probed in amorphous Ge2Sb2Te5 attributed to a structural defect at a specific energetic distance to
the band edge. To still achieve a coherent DOS, the authors had to choose clearly different capture characteristics
for the peak compared to the continuous spectrum of localised states. Observing two features in the DOS with
considerably different capture characteristics means that the MPC signal is a superposition of two different MPC
signals. If the different contributions to such an ambiguous MPC signal are not separated correctly, the analysis
yields falsified results for the MPC DOS and corresponding capture coefficients. To avoid such a
misinterpretation of experimental data in the following, MPC scans attributed to the continuous spectrum of localised states
are evaluated separately from those MPC scans that show signs of a curvature.
Continuous spectrum of localised states. When compared to existing MPC studies36,44,49,50, the results
from Fig.?1 might already provide an acceptable overlap of MPC scans attributed to the continuous spectrum of
localised states. However, as it turned out during the analysis of both materials, the value of kcNE V ensuring an
optimally coherent MPC DOS seems to vary along the spectrum by at least one order of magnitude. This might
already indicate that the assumption of a constant capture coefficient cannot be maintained. Still, the process
applied so far of visually judging whether the single MPC scans overlap and form a coherent DOS appears to be
strikingly imprecise for properly challenging the assumption of cp = const. Thus, we objectified this procedure to
achieve a more quantitative MPC analysis procedure, wherein the MPC DOS is divided into numerous slices
(Abcincos)r.dAinpgrteocitsheisvaallugeorfoitrhkmc N,MEVPiCsthDeOnScadlactualaptoeidnltosctahlalyt aforer ereaccohrbdiendbayt adnifafelgreonrittthemmpperoragtruarmesmaenddifnouMnAdTiLnAthBe.
same MPC DOS bin are scaled to meet at a common energy level (see methods).
Figure?2 shows the result of the proposed quantitative MPC analysis for challenging the assumption of
cp = const. Since no MPC scans are excluded due to the appearance of a defect in the case of Ag4In3Sb67Te26, the
amount of MPC DOS data being scaled by overlapping is considerably larger compared to the Ge2Sb2Te5 data set.
Apart from this, in both materials the MPC DOS of the continuous spectrum of localised states is still found to
decrease exponentially towards the bandgap center (see left panels of Fig.?2). More importantly, the product kcNE V
increases by more than one order of magnitude when moving from the band edge towards the bandgap center
(see right panels of Fig.?2). This gradient inkcNE V does not appear to be a matter of temperature as all MPC data
points follow a coherent behaviour, regardless of the temperature they were measured at. Since NE V marks the
DOS at the band edge and therefore is a constant reference point for all localised states, the increase in kcNE V
towards the bandgap center must arise from an increase in the capture coefficient for holes cp(T) = kc ? T1/2 of the
probed localised states. This striking observation quantitatively confirms the above mentioned indication for a
non-constant capture coefficient along the continuous spectrum of localised states.
This result clearly conflicts with existing MPC spectroscopy work on amorphous Ge2Sb2Te5 and in general
amorphous PCM42?44, which has always been restricted to the assumption of cp = const. and in which MPC data
has given no reason to hypothesise locally varying capture coefficients. Compared to existing studies (e.g.36,44,49,50),
the newly introduced quantitative matching algorithm in our study benefits from the high signal-to-noise ratio,
large data point density in the frequency domain and small temperature step size between MPC scans. Moreover,
the present work proves the necessity to include a flux-dependent analysis of the MPC signal as preceeding step,
which is not given for previous studies.
With respect to the compelling experimental evidence for non-constant capture characteristics in the
continuous spectrum of localised states, it has to be noted that the currently applied MPC analysis still relies on a
framework in which cp is treated as energy-independent constant29. Since this assumption turns out to be invalid
in the present case, the results shown in Fig.?2 must not be used to extract any concrete DOS characteristics. For
now, the only conclusion regarding the continuous spectrum of localised states that can be drawn based on our
MPC spectroscopy results is that the capture coefficient is non-constant.
In view of this outcome, extracting concrete DOS characteristics for amorphous PCM from MPC
spectroscopy data would require that the true functional dependence of cp for the continuous spectrum of localised states
would be included in the analysis. This task could be approached by identifying an underlying mechanism of
charge carrier trapping and emission that has been absent in MPC studies so far and that implies inhomogeneous
capture characteristics. The involvement of multiple phonons in the transitions to and from localised states as
described by Mott and Davis is a potential candidate for such a mechanism51. According to related studies by
Baranovskii et al. on glassy semiconductors52?54, the multiphonon nature of charge carrier transitions between
bands and localised states causes the probability for such transitions to decrease exponentially with increasing
energy distance. This exponential energy dependence could be considered as additional factor in the capture
coefficient cp. In principle, the current MPC analysis framework could be extended towards such an exponential
energy dependence of cp, but establishing an analytical link between the DOS and the experimental MPC data
becomes less straightforward (see section?S6 in Supplement). Eventually, a revised MPC analysis starting out from
the present work might turn out to require the application of numerical methods.
Localised states attributed to a structural defect. As mentioned above, MPC scans recorded for
amorphous Ge2Sb2Te5 at temperatures around 200 K exhibit a curvature presumably due to a structural defect at
a specific energetic distance to the band edge. Recent computations show that under- or over-coordinated
Ge-atoms could constitute the majority of defects in the bandgap of amorphous GeTe25?27. In this light, it seems
plausible that we find said curvature only in our MPC scans for Ge2Sb2Te5 and not for Ag4In3Sb67Te26 as
germanium-free PCM. Regarding the observed curved shape, it is noticeable that MPC scans presented by
Longeaud et al. on one of the defects in GeTe42 are characterised by a bell-shaped peak, while MPC scans in the
present work only exhibit a slight curvature. Inspecting the four MPC scans at T = 195 K ? 210 K (see Fig.?3)
reveals that the outer parts of the MPC scans seem to follow a strictly exponential decrease, which suggests that
some contribution by the localised states of the continuous spectrum is still present in these MPC scans.
Subtracting the exponential decrease amplifies the curvature and thus helps to determine a suitable value for
kcNE V resulting into satisfying overlap of MPC scans. As a result, the MPC scans from T = 195 K ? 210 K are
scaled with kcNE V = 2 ? 1010 s?1 K?1/2 eV?1, leading to a peak position at approximately 0.25 eV. This energetic
position relative to the band edge agrees well with previous MPC spectroscopy studies43,44,48,55. However, the
above identified necessity to revise the current MPC analysis framework means that also absolute numbers
derived for the defect in amorphous Ge2Sb2Te5 regarding position and capture coefficient must be treated with
Even though a revision of the current MPC analysis seems necessary before quantitative DOS characteristics can
be extracted from our MPC results, we can already report two significant findings regarding the DOS of
amorphous PCM. These are a) the observation of a non-constant capture coefficient for a spectrum of localised states
in the bandgap of both studied materials and b) the apparent lack of a structural defect at a specific energetic
distance to the band edge below the Fermi level in amorphous Ag4In3Sb67Te26. These two findings are
particularly relevant for subthreshold electrical transport. Current PF-based transport models for amorphous PCM only
include trap states at a single energy level. For well-known PCMs like GeTe or Ge2Sb2Te5, it has been possible
to both observe such localised electronic states (for example by MPC spectroscopy42,43) and attribute them to
structural defects involving germanium atoms25,26. In the scenario of germanium-free Ag4In3Sb67Te26 apparently
lacking such a singular defect as main channel for charge carrier emission, a realistic electrical transport model
would need to account for trap- and release processes of charge carriers with a continuous spectrum of
localised states. Such a revised transport model would also have to consider our finding of non-constant capture
coefficients among the continuous spectrum of localised states, which indicates that some states in the bandgap
interact more strongly with charge carriers than others. These conclusions on subthreshold electrical transport in
amorphous Ag4In3Sb67Te26 should also be of importance for the technologically highly relevant threshold
switching in amorphous PCM. While popular threshold switching models so far rely on trap centers at a single energy
level56,57, it appears likely in view of the above that not only subthreshold conduction, but also threshold
switching in Ag4In3Sb67Te26 demands a different explanation accounting for the presence of a continuous spectrum of
localised states. Ultimately, a transport model that is able to explain the typical current-voltage characteristics of
amorphous PCM as a consequence of a continuous spectrum of localised states within the bandgap should be
applicable also to PCMs like GeSbTe and might thus render the existence of sharp defect levels less relevant for
the observed electrical properties.
experimental. Lateral devices were fabricated for MPC spectroscopy measurements, with 100 nm thick
PCM material (Ag4In3Sb67Te26 or Ge2Sb2Te5) deposited on a substrate in between two tungsten electrodes.
To prevent the fully as-deposited amorphous PCM from oxidising, it was capped in-situ with a 10 nm layer of
(ZnS)80:(SiO2)20. We recorded experimental data by homogeneously illuminating a complete electrically
contacted sample of amorphous PCM. No further areal segmentations of the sample were applied. The active volume
of amorphous PCM between the two electrodes (100 nm by 1.2 mm by 40 ?m) is large compared to potential
spatial fluctuations in the density of localised states. Hence, the measurements are of intrinsically averaging character.
Electrical measurements were conducted in a Janis ST-500-2UHT cryogenic probing station, evacuated to
pressures p ? 1 ? 10?4 mbar. While a Keithley 2400 source meter is used to apply a low-field bias voltage, the device
current is amplified and converted to a voltage signal by means of a Femto DHPCA-100 transimpendance
amplifier. The third essential electronic component of the setup is a HP 3562A signal analyser, which also serves as
signal generator. The modulated, monochromatic light passes through an optical attenuator (type DD-600 by
OZ-optics) and is fed into the cryostat chamber (further details are listed in the Supplement Section?S1). While
existing MPC spectroscopy studies commonly use a Lock-in amplifier to compare excitation signal and MPC
signal (see e.g.41), the HP 3562 A performs a single-point FFT analysis of the input signal, offering a remarkable
measurement speed when measuring the amplitude of the modulated photocurrent |Iac| and its phase shift ?
with respect to the excitation signal. This allows for conducting the flux-dependent MPC spectroscopy described
below in a time-efficient manner.
Before starting the MPC measurement, the optimum fibre position for a most homogeneous sample
illumination was determined following an automated procedure. Subsequently, the signal analyser performed a frequency
sweep (MPC scan) for the modulation frequency ? from 10 Hz to 40 kHz, recording the amplitude |Iac|(?) and
phase shift ?(?) of the modulated photocurrent at various light fluxes (see below) at a specific temperature. This
procedure was repeated for various temperatures (in 5 K steps), as long as a sufficient signal-to-noise ratio was
encountered. Photoconductivity in amorphous PCM commonly exhibits a peak at around 200 K (AgIn-doped
Sb2Te) and 250 K (Ge2Sb2Te5), respectively58,59. MPC scans for temperatures above or below this peak suffer from
decreasing signal-to-noise ratio, additionally impaired by exponential increasing device resistance for decreasing
Flux-dependent MPC spectroscopy. As described in the original MPC analysis based on trap and release
processes by Longeaud et al.29, an analytical expression to relate |Iac|(?) and ?(?) to the density of localised states
can only be obtained if the probed energy levels are unaffected by recombination. Following work of Taylor
and Simmons (e.g.28) and also Shockley and Read60 on occupation statistics in the non-equilibrium steady state,
increasing light flux widens the so-called recombination zone around the bandgap center. We therefore propose
an experimental procedure to identify, which light flux should be used to record data for |Iac|(?) and ?(?) with as
large as possible signal-to-noise ratio and unaffected by recombination.
Recording a first MPC scan with the highest available light flux implies that probably all probed energy
levels are affected by recombination due to a very large recombination zone. Repeatedly recording MPC scans at
decreasing flux shrinks the recombination zone and leads to more and more energy levels (starting with levels
closer to the band edge, which are probed at higher excitation frequencies) being completely unaffected by
recombination. Eventually, the MPC output is independent of further lowering the flux, indicating which particular
MPC scan segment can be used for further MPC analysis. Note that the explicit assignment between excitation
frequency ? and probed energy level E?p is only made in the subsequent analysis as described below. Further
details on this measurement procedure and exemplary raw data for flux-dependent MPC scans can be found in
the Supplement Section?S2.
Analysis for Dos spectroscopy. Two essential expressions, which have been developed by Longeaud et
al.29 and were used also recently for MPC DOS spectroscopy on amorphous PCM42,43, serve as point of departure
for our DOS spectroscopy analysis:
We also take into account that various quantities have implicit temperature dependencies, which is
problematic for the collective analysis of MPC scans measured at various temperatures. Besides the already mentioned
NV ,eff = kBT ? NE V, also the mobility ?ext,p and the capture coefficient cp are expected to have a certain
temperature dependence: ?ext,p = k? ? 1/T (due to phonon scattering, see e.g.62) and cp = kc ? T1/2 (due to the thermal velocity
and assuming temperature-independent capture cross sections), with k? and kc constant in T.
N(E?p) ? cp =
? q?SGac sin(?)
E?p ? E V = kBT ln(?p/?).
Equation?1 relates the recorded MPC signal (|Iac|(?) and ?(?)) to the DOS N at the probed energy level E?p,
with cp denoting the capture coefficient for holes of the probed states, ?ext,p the extended-state mobility of holes,
q the elementary charge, ? the applied electrical field, kB the Boltzmann constant, S the current cross section, Gac
the modulated component of the photogeneration rate and T the sample temperature during the MPC scan. It is
important to note that the MPC signal in equation?1 only relates to the amplitude and phase shift of the
modulated photocurrent, while it remains unaffected by the darkcurrent running through the sample under test. Free
carriers contributing to the darkcurrent do not follow the excitation signal of the illumination and therefore do
not contribute to the MPC signal.
The term on the left side of equation?1 is termed MPC DOS and obtained by gathering all known quantities,
i.e. parameters defining the experimental conditions and measured data, on the right side. Both quantities, the
MPC DOS and the actual DOS, are proportional to each other under the assumption that all involved states have
the same capture coefficient. As it is described in29, this assumption of cp = const. is also essential to linking DOS
and experimental MPC data in equations?1 and 2. Taking into account effects of the inhomogeneous
photogeneration rate in the sample along the penetration depth61, the product S ? Gac can be substituted by l ? Fac with l
denoting the electrode length and Fac the modulated component of the light flux.
Equation?2 relates the excitation frequency ? to the probed energy level with respect to the valence band edge
EV, originating from the fact that these states are probed, whose emission rate of trapped carriers is equal to the
excitation frequency29. The attempt-to-escape frequency for holes ?p is related to the capture coefficient cp and the
effective density of states at the valence band edge NV,eff via ?p = cp ? NV,eff. In amorphous semiconductors the latter
is commonly assumed as NV ,eff = kBT ? NE V42,62, N being the DOS at the valence band edge EV. Eventually, it is
noted that equations?1 and 2 are based on assuminEgV that band transport is the dominating electrical transport
mechanism for photocarriers29. This assumption appears to be justified for modulated photoconductivity data
recorded for the present work (see Supplement Section?S5).
Due to the logarithmic frequency dependence in equation?2, only a narrow part of the MPC DOS can be
probed at a constant temperature, since the range of the modulation frequency is typically limited to three orders
of magnitude. However, the range of probed energy levels can be extended by shifting the scanned energy levels
through a variation of the sample temperature. A coherent picture of the MPC DOS can then be composed from
the MPC scans for various temperatures by matching overlap regions, in which the same energy levels are probed
at different temperatures. This matching is achieved by tuning ?p. The value for ?p most suitable for matching the
data then carries information about the capture characteristics (more precisely the capture coefficient cp via ?p) of
the probed states (see e.g.29,41,43). Hence, the proportionality constant linking the actual DOS N(E?p) to the MPC
DOS on the left side of equation?1 is directly affected by this matching procedure.
For the present study, we propose some modifications of equations?1 and 2. In order to obtain a quantity from
MPC spectroscopy that is linked more directly to the actual DOS N, we bring cp to the right side of equation?1.
This step of eliminating the capture coefficient from the MPC DOS allows us to demand that MPC data points
found in the same MPC DOS bin meet at a common energy level, regardless of the fact that the assumption of
cp = const. might not be valid. As cp is linked to ?p used as matching parameter in equation?2, it makes sense to
operate with the same quantity in both equations: ?p = cp ? NV,eff. Thus equation?1 is not only divided by cp, but also
by NV,eff resulting in ?p in the denominator of the right hand side of the equation.
NV ,eff(T ) ? ?ext,p(T )
cp(T )NV ,eff(T )
? q?SGac sin(?) .
NE V ? k?
? q?lFac sin(?) .
While the temperature dependencies on the left side cancel each other out, all temperature terms on the right
can be combined in a single T5/2 term. Also, the whole equation is multiplied by the Boltzmann constant kB, which
was introduced through NV,eff before. Our modified MPC DOS (left side of equation? 4) is now
temperature-independent and directly proportional to the actual DOS N(E?p) normalised by the DOS at the
valence band edge NE V. The constant k?, which is treated as unknown in the present case and might be
determined by Hall measurements62, remains as the constant of proportionality between this normalised actual DOS
and the derived MPC DOS.
As the parameter ?p used for matching MPC scans from different temperatures has been replaced by
?p = cp ? NV ,eff = (kcT 1/2) ? (kBTNE V), we are now able to vary only the remaining unknowns without the
temperature dependencies. Hence, while before ?p was varied to match overlapping scans, now the product kcNE V acts
as temperature-independent tuning parameter for the matching process of MPC scans. As a consequence of
making the connection between cp and ?p explicit and dividing equation?1 by cp, the matching parameter is no
longer hidden within the MPC DOS, but instead appears together with all other quantities derived from the MPC
measurements on the right side of equation?4. k?, in contrast, cannot be derived from the MPC data and therefore
remains within the MPC DOS (on the left side of equation?4). The matching parameterkcNE V has a direct effect
on both quantities, the MPC DOS (equation?4) and the energy scale (equation?5):
[E?p ? E V](T ) = r(T ) ? [E?p ? E V](T = 0 K) = kBT ln([kcNE VkBT 3/2]/?).
Here, we indicated also that the energetic distance between probed energy level E?p and valence band edge EV
can be temperature-dependent. In light of Varshni?s widely recognised work63 on the temperature-dependence
of the bandgap EG(T) = EG(T = 0 K) ? ?(T) with ?(T) = ?T2/(T + ?), we follow the argument that the
temperature-induced shrinking of the energetic distance between valence and conduction band edge by a factor
r(T) = (1 ? ?(T)/EG(T = 0 K)) translates into the same relative shrinking of all energetic distances between states
within the bandgap.
As the process of matching MPC scans recorded at different temperatures demands that both derived
quantities, i.e. MPC DOS and energy scale, are temperature-independent, the mentioned temperature dependency of
E?p ? EV is transferred to the right side of equation?5 leaving the left side with the energy scale E?p ? EV at T = 0 K:
[E?p ? E V](T = 0 K) =
kBT ln([kcNE VkBT 3/2]/?)
kBT ln([kcNE VkBT 3/2]/?)
1 ? ?(T )/EG(T = 0 K)
For the parameters ? and ? in ?(T) we used the values determined experimentally in our earlier publication47.
While results in Fig.?2 are presented for the energy scaling in equation?6, gaps in existing research leave leeway for
alternative scenarios of energy scaling. However, complementary MPC evaluations in Supplementary Section?S3
relying on alternative energy scalings indeed yield the same key result of a non-constant capture coefficient for the
spectrum of localised states in the bandgap.
Composing the MPC DOS. Starting from an initial value for the product kcNE V chosen uniformly for all
energy levels, this initial value might be locally too high or too low to achieve overlap of neighbouring MPC scans.
The essential task of the following MPC analysis is to find the actual product(kcNE V) = ? ? kcNE V to locally
optimise overlap by determining the factor ? separately for thin slices of the MPC DOS. Considering one of these
MPC DOS bins, an algorithm programmed in MATLAB checks for data points that describe the same MPC DOS
(at least within the sufficiently narrow bin width). The found data points are most likely not scaled precisely to the
same energy level by the initial kcNE V value, hence the factor ? has to be chosen in a way that the MPC data points
found in this bin are scaled to the same energy level, Thereby, changing the productkcNE V does not only move the
data points along the x-axis ([E?p ? EV](T = 0 K)), but also affects the y-axis (N(E?p)/NE V ? k?). The scaling
algorithm includes parametrisation of MPC data points, so that the number of involved measurement points for
determining the factor ? per bin lies in the general order of 102. Further details on this MPC DOS composition
procedure can be found in the Supplementary Section?S4.
The data that support the findings of this study are available from the corresponding author upon reasonable
The research leading to these results has received funding from the People Programme (Marie Curie Actions)
of the European Union?s Seventh Framework Programme FP7/2007-2013/ under REA grant agreement No
610781, from the European Research Council (ERC) under the European Union?s Horizon 2020 research and
innovation programme (grant agreement No 640003), and from Deutsche Forschungsgemeinschaft (DFG)
through the collaborative research centre Nanoswitches (SFB 917). Furthermore, the authors acknowledge
insightful discussions with C. Longeaud during the analysis of the data. Finally, support from IBM Zurich of
P. Jonnalagadda and W. Koelmans with sample fabrication and M. Le Gallo and U. Egger with the design and
handling of the measurement setup is gratefully acknowledged.
M.S., M.R. and D.K. conceived the study, M.R. and A.G. designed and conducted the experiment with support of
A.S. M.R., A.G. and M.S. analysed the results. M.R. wrote the manuscript supported by M.S. All authors reviewed
Supplementary information accompanies this paper at https://doi.org/10.1038/s41598-019-43035-7.
Competing Interests: The authors declare no competing interests.
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