This application claims the right of priority of European Patent Application No. EP 23173681.0, filed May 16, 2023, the contents of which are incorporated by reference herein in its entirety.
The present invention concerns a method, a computer program as well as a system for determining respective transport properties of majority as well as minority charge carriers in a sample.
The development of novel and improvement of existing semiconductor and semi-insulating materials relies on the precise knowledge of free-charge transport properties. In particular, knowledge of minority and majority charge carrier diffusion lengths, lifetimes, mobilities, and carrier densities allows for tailoring the design of semiconductor devices and control effectiveness of solar cells, transistors, detectors, sensors, and LEDs. At the moment, the detection of minority and majority charge properties, i.e. of electrons and holes or vice versa, is challenging due to the limitation of the experimental methods. The methods, such as time-resolved photoluminescence (trPL), can detect a lifetime for only a minority of carriers, which control the fast decay component of the signal. The additional drawback of the commonly used methods is that they probe charge carriers' properties in a transient regime which is not matched with device or material operation conditions in a steady state. Therefore, there is a demand for probing the charge carrier properties, that include separate holes and electron carrier densities, lifetimes, diffusion length, and mobility, particularly under steady state conditions, in order to characterize semiconductor materials and -devices.
The Hall effect, which is a reaction of the material on the magnetic field, was discovered by Edwin Hall in 1879. The Hall effect voltage is proportional to the strength of the magnetic field and the applied electrical current. Hall described the reaction of gold films on the magnetic field and considered only one carrier type—the electron. In the twentieth century, it was demonstrated that a combination of light and the Hall effect could be used to access electron and hole signals in semiconductors due to the unique feature of the Hall effect signal consisting of contributions of both holes and electrons. On the other hand, this approach had limiting implications due to the unknown value of electron and hole mobility which have not allowed resolute carrier transport parameters. Recently, several studies used a single carrier regime assuming an equal charge carrier density of holes and electrons to assess the properties of carriers in general. Methods for measurements of photogenerated charge carriers by the Hall method were presented (U.S. Pat. No. 10,197,640 B2, US2021262982A1), wherein the charge carrier density of holes and electrons and their lifetimes were assumed to be equal for any light intensity. However, particularly in semiconductors, the carrier densities, lifetimes, and diffusion lengths of electrons and holes are not equal due to the presence of traps. Assuming the same charge carrier density of holes and electrons therefore leads to incorrect charge transport description.
Based on this, it is subject of the present invention to provide a method, a computer program as well as a system that allows reliable determination of transport properties of majority as well as minority charge carriers, respectively.
This task is solved by a method for determining respective transport properties of majority as well as minority charge carriers with the features of claim 1 as well as a corresponding computer program with the features of claim 14 and a corresponding system with the features of claim 15.
In the following, examples of the present invention and its preferred embodiments are described with reference to the accompanying drawings.
Advantageous embodiments of the invention are given in the corresponding dependent claims and described in the following.
The first aspect of the invention relates to a method for determining respective transport properties of majority as well as minority charge carriers in a sample comprising the majority and the minority charge carriers that correspond to electrons and holes or vice versa. In the method according to the first aspect of the invention, a plurality of Hall measurement trials is performed on the sample, wherein during each Hall measurement trial, the sample is exposed to an illumination intensity I, and a Hall coefficient and a conductivity are acquired from each Hall measurement trial.
In or during a first Hall measurement trial of the plurality of Hall measurement trials, the sample is exposed to a first illumination intensity I1, in the range of zero to 0.02 suns, particularly wherein the first illumination intensity is zero, and
In or during a second measurement trial of the plurality of Hall measurement trials, the sample is exposed to a second illumination intensity I2 and
A third carrier mobility μ3 is determined from the first and the second carrier mobility, particularly by subtracting the second carrier mobility from the first carrier mobility if the Hall coefficient has the same sign for the first and the second illumination intensity or by adding the second carrier mobility to the first carrier mobility if the Hall coefficient changes its sign for the first and the second illumination intensity.
The first carrier mobility μ1 is assigned to, particularly corresponds to a mobility of the majority charge carriers, μ2 is assigned to, particularly corresponds to the absolute value of the difference between hole and electron mobility, and the third carrier mobility μ3 is assigned to, particularly corresponds to a mobility of the minority charge carriers in the sample.
Generally, the sample, particularly a semiconductor, comprises majority as well as minority charge carriers by means of electrons and holes or vice versa. However, their contribution to conduction depends strongly on the illumination intensity to which the charge carriers are exposed. Particularly, for low illuminations I1, particularly at zero illumination, the contribution of the majority charge carriers may be so large that the influence of the minority charge carriers on conduction is negligible. As the illumination intensity is increased from I1, the contribution of the minority charge carriers to conduction increases towards a regime around I2, where the charge carrier density of majority and minority charge carriers are essentially identical.
Particularly, the first illumination intensity is zero.
The term “identical” preferably comprises deviations between the charge carrier densities of the majority and minority charge carriers within the range of 0.01% to 15%, which arise as a consequence of the large charge carrier densities, that are typically between 1013 to 1017 cm−3 for illuminations between 0.02 sun and 10 sun.
The respective charge carrier densities of the majority or minority charge carriers include a respective dark charge carrier density at the first illumination, particularly at zero illumination intensity as well as a respective photogenerated charge carrier density due to photogenerated charge carriers at the second illumination intensity.
Experimentally, converging, particularly identical charge carrier densities generally show by means of at least a partial cancellation of the contributions of the majority and the minority charge carriers to the Hall coefficient, such that the Hall coefficient asymptotically approaches zero as the illumination is increased into the regime around I2. The Hall coefficient asymptotically approaching zero is thus one of the signatures for identical charge carrier densities. The term “asymptotically” means that increasing the illumination intensity from one illumination intensity value in predefined increments to higher illumination intensity values goes along with smaller changes in the absolute value of the Hall coefficient for every consecutive increment within the accuracy of the measurement.
Particularly, from the acquired conductivity and the Hall coefficient, particularly wherein the Hall coefficient is obtained from RH=VHd/(I0B) with I0 the applied electrical current, B the magnetic field amplitude, d the thickness of the sample; a Hall mobility may be determined for a given illumination intensity, μH(I)=σ(I)RH(I), particularly for I=I1 or I2.
Particularly, for increasing illumination intensities, the conductivity increases, while the Hall coefficient shows an asymptotical approach towards zero. The second Hall mobility, that is, the Hall mobility at the second illumination intensity, may be obtained from the product of the conductivity and the Hall coefficient at the second illumination intensity. At I2, the increase of the conductivity and the asymptotical approach towards zero of the Hall coefficient result in an asymptotical approach of the Hall mobility toward a constant value. Particularly, I2 is so high that the Hall mobility shows an asymptotical approach by means of a saturation-like rise, towards a constant value for I2. for example for Si-based samples. For other samples, for example, Perovskite-based samples, the Hall mobility shows an asymptotical approach by means of a depletion-like drop towards a constant value for I2. The Hall mobility shows an asymptotical approach towards a constant value for I2 is thus the second signature for identical charge carrier densities.
Particularly, I2 is higher than 0.02 suns, more particularly higher than 0.1 suns.
In the case of a sample with one of the two carrier types having a significantly larger mobility than the other one, for example p-type doped Silicon with much larger electron mobility compared to the hole electron mobility, identical charge carrier densities of the majority and the minority charge carriers leads to a saturation of the Hall mobility in the regime of I2, accompanying the asymptotical approach to zero of the Hall coefficient. Hence, the second illumination intensity I2 may be chosen so high that for I2. i) the second Hall coefficient asymptotically approaches zero and ii) the Hall mobility approaches a constant value, within deviations of less than 10% compared to the constant value. Due to the much larger mobility of electrons, the Hall coefficient first drops steeply as the illumination is increased from I1 and changes its sign from positive to negative. If the illumination is further increased towards I2, the Hall coefficient features the characteristic asymptotical approach, particularly decreasing towards zero. As such, the steep drop of the Hall coefficient in the illumination regime where the sign is changed is not to be confused with the smooth, asymptotic approach towards zero, such that I2 may be selected from this illumination regime.
In the case of a sample with one of the two carrier types having a similar mobility compared to the other one, for example a p-type halide perovskite semiconductor with similar electron and hole mobility, identical charge carrier densities of electrons and holes show by means of a monotonic, asymptotic decrease of the Hall coefficient to zero or below the lower sensitivity limit of the lock-in amplifier and source meter, where electrons and holes completely compensate each other, allowing to select a value for I2 from this regime. Particularly, for perovskite, the Hall coefficient takes on only one sign between the first and the second illumination intensity.
The sample may comprise an essentially planar structure, particularly a semiconductor structure, that can be grown epitaxially, and/or spin coated, and/or air blade coated, and/or dip coated, and/or inkjet printed, and/or vapor deposited, and/or ultrasonic sprayed and/or comprise features manufactured lithographically. These kinds of samples typically comprise small vertical dimensions, herein also referred to as a thickness d. compared to their lateral dimensions, herein also referred to as the width and length of the sample. Consequently, the sample may comprise two main surfaces extending along the lateral dimensions of the sample.
The Hall measurement trial is preferably understood as a Hall measurement, wherein a current, particularly a constant current, is applied between two contacts on the sample and wherein a magnetic field is applied particularly perpendicular to the current. In particular, the magnetic field is applied perpendicular to the main surfaces of the sample. The sample may comprise at least four, particularly exactly four or exactly six electrical contacts, particularly Ohmic contacts, for performing electrical measurements on the sample. To this end, the sample may comprise conductive regions in the shape of a Hall bar with the contacts arranged in peripheral arms of the Hall bar or four-point probe placed around the perimeter of the sample. The Hall voltage for acquiring the Hall coefficient is preferably determined by acquiring the electrical voltage between two contacts arranged perpendicular to the current flow and the magnetic field, which is caused by charge carriers that are deflected by the Lorentz force. The ratio between the Hall voltage and the applied current defines a Hall coefficient, RH=VHd/(I0B). Moreover, during the Hall measurement trial, a longitudinal voltage Vxx between two contacts arranged along the direction of the current is acquired. From the current, the sample thickness and the longitudinal voltage, a conductivity is determined from σ=I0/(Vxxd). In the case of the 4-probe sample, σ is multiplied by coefficient 0.2207.
Particularly, the mobility of the majority charge carriers is acquired from the Hall mobility at the first illumination intensity, μH(I1)=σ(I1)RH(I1)=μ1. This is because at the first illumination intensity, particularly for zero illumination, the contribution of the majority charge carriers to conduction dominates the acquired measurement signals by means of the conductivity and the Hall coefficient.
To determine the mobility of the minority charge carriers buried in the measurement signals comprising the Hall coefficient and the conductivity, the second mobility is preferably determined from μH(I2)=σ(I2)RH(I2)=μ2.
From the first and the second mobility, the mobility of the minority charge carriers, also
denoted herein as the third mobility, can be determined.
In the case of a sample with minority charge carriers having a larger mobility compared to the majority charge carriers, like for example in p-type Silicon, the third mobility is determined from adding the first and the second mobility, μ3=μ1+μ2.
In the case of a sample with majority carriers having a larger mobility compared to the minority charge carriers, like, for example, in p-type halide perovskite, the third mobility is determined by subtracting the second mobility from the first mobility, μ3=μ1−μ2.
According to an embodiment of the first aspect of the invention, if RH(I1)>0, the majority charge carriers are holes and the minority charge carriers are electrons and wherein if RH(I1)<0, the majority charge carriers are electrons and the minority charge carriers are holes. As such, the majority and the minority charge carrier can be immediately determined from the sign of RH(I1).
The comparison of the majority and the minority charge carrier mobilities (μ1 and μ3) can be initially challenging due to unknown μ3. To resolve this issue, the sign of the Hall coefficient RH(I) is preferably considered between I1 and I2. If between I1 and I2, the sign of RH(I) changes (from − to + or from + to −), then the minority charge carriers have larger mobility compared to the majority charge carriers, as for example in the case of p-type Silicon. If the sign of RH(I) does not change between I1 and I2, then the majority carriers have larger mobility compared to the minority charge carriers, as for example in the case of p-type perovskite.
In an embodiment of the first aspect of the invention, one or more intermediate Hall measurement trials are executed, wherein for each of the intermediate measurement trials the sample is exposed to a differing illumination intensity, wherein the illumination intensity of each intermediate measurement trial lies between the first illumination intensity I1 and the second illumination intensity I2, wherein an intermediate Hall coefficient and an intermediate conductivity are determined for each intermediate measurement trial, particularly wherein the Hall coefficient RH and the conductivity σ is determined as a function of the illumination intensities I from the plurality of Hall measurement trials.
Further Hall measurement trials can be performed for intensities larger than I2 to study charge transport properties at higher intensities.
Particularly, one or more intermediate Hall measurement trials are comprised of the plurality of Hall measurement trials.
Preferably, for each of the one or more intermediate Hall measurement trials, the sample is exposed to a different illumination intensity. For example, starting from the first illumination intensity, the illumination intensity may be increased up to the second illumination intensity, wherein intermediate Hall measurements are performed for discrete illumination intensities in the range between I1 and I2. For example, intermediate Hall measurements may be performed at between 5 to 100 or between 100 to 1000 illumination intensities between I1 and I2. As such, the Hall coefficient and the conductivity σ may be obtained as a function of the illumination intensity, VH(I) and σ(I), in the range set by I1 and I2.
According to another embodiment of the first aspect of the invention, a minority charge carrier density n3 is determined, particularly as a function of the illumination intensity I, from the conductivity σ(I), a Hall coefficient Ry as well as the first and the third mobility μ1, μ3, particularly from
if holes are the majority charge carriers, so that n3 represents the charge carrier density of the minority charge carriers, that is, electrons, and from
if electrons are the majority charge carriers, so that n3 represents here the charge carrier density of the minority charge carriers, that is, holes, with q being the elementary charge.
In yet another embodiment of the first aspect of the invention, a majority charge carrier density n1 is determined, particularly as a function of the illumination intensity I, from the conductivity σ, the minority charge carrier density n3, as well as the first and the third mobility μ1,3, particularly from
According to another embodiment of the first aspect of the invention, at least one of the following transport properties is determined as follows, particularly as a function of the illumination intensity I:
a total Quasi-Fermi level splitting QFLStotal based on the sample temperature T, the majority and the minority charge carrier density n1,3, particularly from QFLStotal=kBT ln(n1n3/nint2)/q where nint=√{square root over (n1(G=0)n3(G=0))} is an intrinsic carrier density, and
wherein QFLSB,A are total Quasi Fermi level splitting determined at two different generation rates GA,B, respectively, particularly wherein the two generation rates GA,B differ from each other by at least 25% and GB>GA.
In an embodiment of the first aspect of the invention, if the Hall coefficient RH(I) and the conductivity σ(I) are altered by a parasitic conductivity σs, such that an acquired Hall mobility μH(I)=RH(I)σ(I) comprises a peak value max(μH(I)) with max(μH(I))>μH(0), particularly with max(μH(I))>μ1, a corrected majority charge carrier density at the first illumination intensity, particularly at zero intensity, n1,corr(I=0) accounting for parasitic contributions σs to the first conductivity σ(I1) is determined based on the first conductivity σ(I1) and μH(I), particularly from n1,corr(I=0)=μH(I1)σ/(q(max(μH(I)))2), and/or wherein a corrected first mobility μ1,corr is determined based on μH(I), particularly from μ1,corr=max(μH(I)).
Generally, parasitic conductivity shows by means of a peak of the measured Hall mobility as a function of the illumination intensity μH(I). For example, in the case of Perovskite, the Hall mobility typically comprises a single peak between I1 and I2, such that the peak value in this example can be particularly found from max(μH(I)).
However, samples may also exhibit a hybrid behavior between Silicon and Perovskite, which may cause a plurality, particularly two peaks between I1 and I2. In this case, the parasitic conductivity is preferably determined from the first peak value of μH(I) as the intensity is increased from I1.
Particularly, the peak value can be determined or identified from considering the derivative of the Hall mobility as a function of the illumination intensity. In particular, the peak value can be determined or identified by searching the point where the derivative of the Hall mobility is at or around a minimum, particularly at or around zero.
According to another embodiment of the first aspect of the invention, the parasitic conductivity σs is determined based on the first conductivity σ(I1), the corrected first mobility μ1,corr and the corrected majority charge carrier density n1,corr(I1), particularly from σs=σ(I1)−qμ1,corrn1,corr(I1).
In yet another embodiment of the first aspect of the invention, if
Particularly, μ3 is determined by adding the first and the second charge carrier mobility if β<0 and (μH(ID)<μH(IC)), or if β>0 and μH(ID)>μH(IC) and μ3 is determined by subtracting the second charge carrier mobility from the first charge carrier mobility, if β>0 and μH(ID)<μH(IC).
According to an embodiment of the first aspect of the invention, if the acquired Hall coefficient RH(I) comprises a signal-to-noise ratio of less than 1 and if the majority and the minority charge carriers are both photogenerated by the same amount, Δn1(ΔI)=Δn3(ΔI), such that their respective photogenerated charge carrier densities are equal and determined based on σ and σ(I=0) as well as μ1 and μ3, particularly from
In another embodiment of the first aspect of the invention, if the acquired Hall coefficient RH(I) comprises a signal-to-noise ratio of less than 1 and if only the majority charge carriers are photogenerated, such that only n1 (and not n3) changes as a function of the illumination intensity, n1 is determined based on σ(I) and μ1, particularly from
The formulation “that only n1 changes as a function of the illumination intensity” is preferably understood such that n1 does change as a function of the illumination intensity and n3 does not.
According to another embodiment of the first aspect of the invention, the illumination is provided by means of a continuous electromagnetic wave, particularly using a light emitting diode (LED) or a laser diode (LD).
In yet another embodiment of the first aspect of the invention, the sample is comprised by a semiconductor device or a component of the semiconductor device, such as a solar cell, an interface, a transistor, a photodetector and/or a diode, wherein the respective transport properties of the majority as well as minority charge carriers of the sample comprised by the semiconductor device are characterized.
A second aspect of the invention relates to a computer program comprising instructions which, when the program is executed by a computer, cause the computer to carry out the method according to the first aspect of the invention.
A third aspect of the invention relates to a system for determining respective transport properties of majority and minority charge carriers in a sample comprising the majority and the minority charge carriers that correspond to electrons and holes or vice versa. The system is configured to determine the respective transport properties using the method according to the first aspect of the invention and/or using the computer program according to the second aspect of the invention.
According to the third aspect of the invention, the system comprises:
Particularly, the embodiments of the first aspect of the invention apply to the second and/or the third aspect of the invention.
Exemplary embodiments are described below in conjunction with the Figures. The Figures are appended to the claims and are accompanied by text explaining individual features of the shown embodiments and aspects of the present invention. Each individual feature shown in the Figures and/or mentioned in the text of the Figures may be incorporated (also in an isolated fashion) into a claim relating to the method, the computer program and/or the system according to the first, second and the third aspect of the present invention.
The sample 107 is loaded using 4-probe or 6-probe contact geometry card 202 electrically connected with the first current source 205, the current meter 206 and the source meter 207. The first current source 205 applies the electrical current through the sample. The applied electrical current is measured by the current meter 206. The source meter 207 probes the longitudinal voltage Vxx for the calculation of the conductivity from σ=I/(Vxxd) as well as the Hall voltage VH for the calculation of a corresponding Hall effect coefficient RH=VHd/I0B, with I0 the applied current and B the applied magnetic field. The voltages are measured at the output of the lock-in amplifier 204. The sign of the Hall coefficient is detected from the phase of the measured signal.
According to the invention, a first Hall measurement trial is performed at a first illumination intensity I1 that is lower than 0.02 suns, particularly wherein the first illumination intensity is zero. In other words, the first Hall measurement is preferably performed in the dark. A second Hall measurement trial is performed at a second illumination I2 that is chosen so high that the charge carrier density of both electrons and holes in the sample are essentially identical. Particularly, intermediate Hall measurement trials are performed at intensities between I1 and I2. The Hall measurement trials at finite, nonzero illumination intensities are performed to unlock the charge transport properties of both the majority and the minority charge carriers, since in the dark, the contribution to conduction essentially corresponds to the majority charge carriers. To this end, in this embodiment the sample is continuously illuminated by the LED 109. The illumination intensity is controlled by an electrical current applied to the LED 109 by the second current source 208. The skilled person will appreciate that the illumination intensity may also be provided and controlled by alternative light sources, such as for example a laser system, an optical fibre laser or a monochromator. All instruments are driven by the computer program 211 executed on the computer 214, which is in turn controlled by a user input 213 where the user can set the illumination intensities to and between I1 and I2, as well as an amplitude and frequency of the applied magnetic field, a duration of the individual Hall measurement trials, the current applied through the sample, lock in amplification parameters of the lock-in amplifier 204, and a number of intermediate Hall measurement trials to be executed between I1 and I2. The user input may also 213 allow for entering the sample thickness, which is used to calculate some of the transport properties. The user can also select the value of μ1 and μ2 from the acquired dependence of Hall mobility on the illumination intensity, μH(I). As a result of this selection, the computer program will recalculate the charge carrier density and charge carrier transport properties according to the selected values. In particular, the user can select correction algorithms 500, 900, 1000 disclosed below and apply them to see the effect of the correction algorithms 500, 900, 1000 on outputs 215, 313 of the method provided by the system 100. The sample 107 shown in block 202 of
The voltages are preferably acquired for both negative and positive applied currents and negative and positive magnetic fields, so that a non-uniformity of the sample 107 is minimized. The values acquired for negative and positive currents or magnetic fields are preferably averaged, as well as the voltages probed on the different contacts. For example, Vxx=(0.5(V12I+−V12I)+0.5 (V24I+−V24I)+0.5(V34I+−V34I)+0.5 (V13I+−V13I))/4). In the case of considerable voltage offset on the contacts, the voltage offset measured at a zero current and/or a drifting baseline voltage is preferably subtracted for both Vxx and {right arrow over (V)}H.
As an output 215 from the Hall measurement trials, the user receives the following transport properties: a majority and the minority charge carrier density n1,3, a majority and the minority charge carrier mobility μ1,3, a majority and the minority charge carrier lifetime τ1,3, a majority and the minority charge carrier diffusion length L1,3, a majority and the minority charge carrier diffusion coefficient D1,3, a Quasi-Fermi level splitting of the majority and the minority charge carriers QFLS1,3, an ideality factor η. The output in particular indicates abovementioned parameters as a function of illumination intensity or generation rate. Particularly, besides the majority and the minority charge carrier mobility that are independent of the illumination intensity, these transport properties are output as a function of the illumination intensity or the charge carrier density. The output 215 and 313 can also comprise data indicative of the conductivity σ, the Hall voltage VH or a Hall coefficient RH=VHd/I0B, a Hall mobility μH(I)=σ(I)RH(I), a parasitic conductivity σs and/or a dark charge carrier density n1,corr(I=0) can be output to the user by the output 215 and 313. The output 215 and 313 may for example be realized by means of a user interface or a screen that shows the transport properties particularly in a graphical representation to the user.
Next, in step 402, the longitudinal voltage Vxx and Hall voltage VH are measured as a function of the generation rate, particularly of the illumination intensity, to find the Hall coefficient, the conductivity, and the Hall mobility as a function of the illumination intensity.
From the Hall coefficient and conductivity, particularly the Hall mobility as a function of generation rate, the majority and the minority charge carrier mobilities are found. The majority carrier mobility is found at the first illumination intensity I1, particularly in the dark. Here, the measured Hall mobility corresponds to the majority charge carrier mobility μH(I1)=μ1.
In step 405, the absolute value of the difference between majority (μ1) and minority charge carrier mobility (μ3), μH(I2)=μ2=|μ1−μ3|, is found at high intensities, particularly at I2, where the charge carrier density of holes and electrons are essentially identical. For intensities in the regime of I2, it is a signature of identical charge carrier densities of electrons and holes that the Hall coefficient asymptotically approaches zero, cf.
In step 407, from the majority charge carrier mobility, particularly of holes, determined in step 403 at I1 and the absolute value of the difference between the majority and the minority charge carrier mobility determined at step 405 at I2, the minority charge carrier mobility is found.
In the case of parasitic conductivity, correction step 406 using a correction algorithm 900 is applied to calculate corrected values for i) the mobilities of the minority and majority charge carriers, ii) the charge carrier density at low illumination, particularly in the dark, and iii) the parasitic conductivity. The correction algorithm 900 is further illustrated in the flowchart of
The next steps include the calculation of the majority and minority charge carrier diffusion coefficient in step 408 using the now known values of the majority and minority charge carrier mobility. The charge carrier density of the majority and minority charge carriers is calculated in step 410 using equations 3-4.
In the case of a low Hall signal, particularly for signal-to-noise-ratios of less than one, which is particularly the case if the majority and minority charge carrier mobilities are similar, correction steps 409 and 411 are performed to find the photogenerated charge carrier density using correction algorithm 1000, which is further illustrated in the flowchart of
From the known charge carrier densities n1,3, mobility μ1,3 and diffusion coefficient D1,3, the transport properties lifetime and diffusion length can be found for electrons and holes separately in step 412. Moreover, the Quasi-Fermi level splitting (QFLS) and the ideality factor can be further calculated in step 412 to predict the performance of the investigated sample 107. particularly the studied semiconductor, as an active material particularly in a solar cell.
As for the embodiment of
in the case of an undetectable Hall effect signal.
In step 903, the corrected majority charge carrier density at zero illumination is found from n1,corr(I=0)=μH(I1)σ/q(μ1,corr)2, wherein I1 is preferably chosen to be zero, and the parasitic conductivity is calculated from σs=σ(I1)−qμ1,corrn1,corr(I1). Subsequently, in step 904, the absolute value of the difference between hole and electron mobility is calculated from respective Hall mobilities and conductivities acquired at two different intensities IC and ID from
wherein μ3 is determined by adding the first and the second charge carrier mobility if β<0 and (μH(ID)<μH(IC)), or if β>0 and μH(ID)>μH(IC) and wherein μ3 is determined by subtracting the second charge carrier mobility from the first charge carrier mobility, if β>0 and μH(ID)<μH(IC).
Upon correction of the majority charge carrier mobility in step 905, the method and/or computer program shown in the embodiment of
in step 1002.
Particularly, in general, to determine the transport properties of the majority and the minority charge carriers the conductivity σ is determined from the applied current lo and the measured longitudinal voltage Vxx, σ=I0/(Vxxd) and the Hall coefficient determined from RH=VHd/I0B are determined experimentally.
To determine the respective transport properties of the majority and the minority charge carriers buried in the acquired conductivity and the Hall coefficient, the experimentally determined conductivity and the Hall coefficient are associated to their theoretical equivalents given by equations 1 and 2:
The charge carrier densities of majority and minority charge carriers can be found using equations 3 and 4 by resolving the conductivity and the Hall coefficient equations, as the impact of majority and minority charge carriers is combined (Eq. 1) and subtracted (Eq. 2), respectively.
To resolve the majority and minority charge carrier densities, the majority and minority charge carrier mobility are needed and can be found from the first Hall measurement trial at the first illumination intensity, particularly at zero illumination, as well as the second Hall measurement trial at the second illumination intensity. The Hall mobility comprising contributions of both the majority and the minority charge carriers (cf. equation 5) is the product of the conductivity and the Hall coefficient μH(I)=σ(I)RH(I).
Equation 5 predicts that the Hall mobility is equal to the majority charge carrier mobility at the first illumination, particularly at zero illumination, cf. also equation 6. Further, the charge carrier densities of the majority and the minority charge carriers are essentially identical at high illuminations on the order of I2. In this illumination regime, the Hall mobility becomes equal to the absolute value of the difference between the majority and the minority charge carrier mobility, cf. equation 6. Using this approach, the majority and the minority charge carrier mobilities can be found.
The majority and the minority charge carrier mobilities are independent of illumination due to the uniform distribution of free carriers. In addition, no experimental evidence for mobility variations was observed, as confirmed by the saturation of the Hall mobility at a constant mobility value shown in
After finding the respective mobilities and charge carrier densities of the majority and the minority charge carriers, the charge transport properties of the majority and the minority charge carriers are calculated using equations 7-10. The generation rate G=P×λ×10−9/(h×c×103×d)) can be determined, preferably in units of cm−3s−1, by calibration of the used LED 109 or by using a pre-calibrated LED 109.
Advantageously, with both the majority and the minority charge carrier densities being known, the respective QFLS1,3 (cf. equation 10) can be determined. The total QFLS can be found summing up QFLS1 and QFLS3, or by QFLStotal=kBT ln(n1n3/nint2)/q. QFLStotal is related to the highest open circuit voltage (VOC) which the examined sample 107, particularly the investigated semiconductor, can support. Practically, this means that the present invention allows to predict the performance of materials as a solar cell absorber, without needing to fabricate and test the full solar cell device. In equation 10, nint denotes the intrinsic carrier density at zero illumination, nint=√{square root over (n1(G=0)n3(G=0))}. Further, from the now known QFLS, the solar cell ideality factor is determined from Equation (11).
Parasitic conductivity, such as surface conductivity, ionic conductivity, grain boundaries conductivity, and conductivity non-uniformities influence the Hall measurement trials by an extra term σs which contributes to the acquired conductance but not to the Hall coefficient or-coefficient due to the low mobility of parasitic charge carriers, which is negligible compared to the mobilities of the majority and the minority charge carriers. Therefore, in case of parasitic conductivity, the Hall mobility and the conductivity must include σs as according to equations 12 and 13.
The impact of free carriers in the bulk of the sample on the conductivity can be boosted to overcome σs by illumination. In such conditions, the contribution of photogenerated majority charge carriers, particularly holes, qμ1n1, will overcome the value of σs and increase up to the value of the actual, corrected majority charge carrier mobility μ1,corr, as predicted by equations 12 to 14.
By finding the majority charge carrier mobility, particularly the hole mobility, as a peak value, μ1,corr=max(μH(I)), the dark conductivity σ(I1=0) and the Hall coefficient can be used to determine the corrected dark majority charge carrier density n1,corr(I=0)=μH(I1)σ(I1)/q(max(μH(I)))2. The parasitic conductivity can then be determined from σs=σ(I1)−qμ1,corrn1,corr(I1).
When the majority and the minority charge carriers have the same or similar mobility values, particularly within 15%, and/or when sample 107 is highly doped so that photogenerated charge carriers do not overcome the dark charge carrier density particularly for n1(I=0)>1014 cm−3, the Hall mobility tends to decrease at higher intensities as the contributions of majority and minority charge carriers cancel each other, which is confirmed by simulations based on equation 12. To neglect the effect of parasitic conductivity on Hall mobility and find minority carrier mobility, neighbor Hall mobility points measured as a function of intensity can be used, particularly wherein the neighbored point are measured at a first intensity IC and a second intensity ID between I1 and I2 and wherein ID exceeds IC by at least 25%.
Thus according to the determined μ2 and β, the value of μ3 is determined by adding the first and the second charge carrier mobility if β<0 and (μH(ID)<μH(IC)), or if β>0 and μH(ID)>μH(IC) and μ3 is determined by subtracting the second charge carrier mobility from the first charge carrier mobility, if β>0 and μH(ID)<μH(IC).
Some materials-such as halide perovskites and organic semiconductors-demonstrate similar values of the majority and the minority charge carrier mobilities, which leads to a very low Hall coefficient as electrons and holes cancel out each other, cf. equation 5. In such conditions, particularly for Hall coefficients with signal-to-noise-ratios below 1, which typically occur at high illumination intensities higher than 0.1 Sun, the photogenerated electron and hole charge carrier densities can be calculated using the conductivity value as shown in equation 15.
To determine the charge carrier properties of the respective sample 107, the sample 107 was exposed to electromagnetic radiation using an LED 109. Both samples 107 were investigated according to the method presented in the embodiment of
In the dark, at zero illumination, the silicon sample features a positive Hall coefficient, and thus a positive Hall coefficient, which proves its p-type conductivity (cf.
The absolute value of the difference between electron and hole mobility, |μ3−μ1|=μ2=1240 cm2V−1s−1 can be found at generation rates G>7×1020 cm−3s−1 where we observe apparent saturation of the Hall mobility due to essentially identical photogenerated charge carrier densities of holes and electrons, cf. equation 6. As a result, the electron mobility value μ3=μe=1568 cm2V−1s−1 is found by adding the hole mobility value. Electron and hole diffusion coefficients De=40.6 cm2s−1 and Dh=8.5 cm2s−1 are assessed using mobilities values and Equation 8.
Now, with the electron and hole mobility, the charge carrier density of holes and electrons can be calculated separately using equations 3-4.
With the revealed charge carrier densities of holes and electrons as a function of the generation rate respective charge carrier properties of both electrons and holes can be calculated using equations 7-10.
The hole lifetime (cf.
Using the values of lifetimes and mobilities, the diffusion lengths can be obtained (cf.
Therefore, the correction algorithm 900 (depicted in
As can be seen in
After applying the correction approach, a hole mobility of 0.55 cm2V−1s−1 is found from the peak value in
The absolute value of the difference between the hole and electron mobility |μ3−μ1|=μ2=0.03 cm2V−1s−1 was found using Equation 14 and neighbor points of the Hall mobility and conductivity. The value of the electron mobility 0.52 cm2V−1s−1 is in full agreement with the initial hypothesis of similar values of hole and electron mobility. Electron and hole diffusion coefficients D3=1.35×10−2 cm2s−1 and D1=1.42×10−2 cm2s are found using perovskite electron and hole mobilities.
The charge carrier densities feature a dominance of holes up to a generation rate 1021 cm−3s−1, after which the charge carrier density of electrons and holes merge, cf.
The carrier lifetimes and diffusion lengths were calculated from the charge carrier densities of electrons and holes (Equations 7-9) and are plotted
The diffusion length, assessed from the lifetime and mobility values, mimics the dependence of lifetime on the generation rate. At one sun power, electrons and holes show similar diffusion lengths L1≈L3=0.48 μm. The steady-state diffusion lengths of the electrons and holes are in good agreement with previously reported values in literature. Finally, the total Quasi-Fermi level splitting and the ideality factor of perovskite were calculated, QFLSpero=1.43 eV and ηpero=1.7. The ideality factor suggests that the non-recombination in perovskite material is similar to Silicon (ηSI=1.66). The diffusion length obtained for perovskites larger than the thickness of the material, pointing to an effective transport of free charges.
Summarizing, for the Silicon and the perovskite sample, fourteen transport properties—n1,3, μ1,3, τ1,3, L1,3 D1,3, QFLS1,3, QFLStotal, and η have been determined as a function of illumination intensity based on the present invention. In contrast, standard Hall effect measurements can provide only two properties: n1 and μ1. In particular, the invention allows to for the first time to distinguish the transport properties of the majority and the minority charge carriers so as to determine respective transport properties of majority and minority charge carriers and their charge carrier densities. Moreover, to overcome the limitation of the CLIMAT method for the perovskite material, an embodiment of the invention successfully provides a correction methods which allows to account for influences of parasitic conductance, doping, and low signal to noise ratios.
The presence of parasitic conductivity decreases the actual value of the simulated Hall mobility at low illumination intensity. By increasing the light illumination, the simulated Hall mobility can be increased up to the value of correct free hole mobility μh=1 cm2V−1s−1. If the electron and hole mobilities are similar, the Hall mobility will then asymptotically decrease from the free hole mobility value so as to approach a constant value corresponding to the difference between hole and electron mobility, cf. equation 6.
The simulations demonstrate that for any material, the Hall mobility asymptotically approaches a constant value, provided I2
Flied on May 9, 2024 is large enough and the measurements comprise a sufficient signal-to-noise ratio such that the asymptotic approach is not buried in noise. Low signal-to-noise ratios typically arise due to highly doped materials, such as Perovskite. Experimentally, for Perowskite, the asymptotic approach may therefore resemble as shown in the data of
Number | Date | Country | Kind |
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23173681.0 | May 2023 | EP | regional |