Analysis of the Voltage Losses in Cztsse Solar Cells of Varying Sn Content Mohammed Azzouzi,†,# Antonio Cabas-Vidani,‡,# Stefan G

Home , Jenny Nelson

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Letter

Cite This: J. Phys. Chem. Lett. 2019, 10, 2829−2835 pubs.acs.org/JPCL

Analysis of the Voltage Losses in CZTSSe Solar Cells of Varying Sn Content Mohammed Azzouzi,†,# Antonio Cabas-Vidani,‡,# Stefan G. Haass,‡ Jason A. Röhr,† Yaroslav E. Romanyuk,‡ Ayodhya N. Tiwari,‡ and Jenny Nelson*,†

† Department of Physics and Centre for Plastic Electronics, Imperial College London, London SW7 2AZ, United Kingdom ‡ Laboratory for Thin Films and Photovoltaics, Empa-Swiss Federal Laboratories for Materials Science and Technology, Ueberlandstrasse 129, 8600 Duebendorf, Switzerland

*S Supporting Information

ABSTRACT: The performance of kesterite (Cu2ZnSn- (S,Se)4, CZTSSe) solar cells is hindered by low open circuit fi voltage (Voc). The commonly used metric for Voc-de cit, namely, the difference between the absorber band gap and fi qVoc,isnotwell-dened for compositionally complex absorbers like kesterite where the bandgap is hard to determine. Here, nonradiative voltage losses are analyzed by measuring the radiative limit of Voc, using external quantum efficiency (EQE) and electroluminescence (EL) spectra, without relying on precise knowledge of the bandgap. The method is applied to a series of Cu2ZnSn(S,Se)4 devices with Sn content variation from 27.6 to 32.9 at. % and a corresponding Voc range from 423 to 465 mV. Surprisingly, ffi the lowest nonradiative loss, and hence the highest external luminescence e ciency (QELED), were obtained for the device with ff the lowest Voc. The trend is assigned to better interface quality between absorber and CdS bu er layer at lower Sn content.

esterite solar cells are a promising earth-abundant poor and Zn-rich. This reduces the formation of detrimental fi K alternative to existing thin lm photovoltaic technolo- defects like interstitials (Cui and Zni) and [2CuZn +SnZn] gies.1 Even though their power conversion efficiencies (PCE) antisite clusters that adversely affect the solar cell performance, have increased significantly during the past decade from 4% in while increasing the concentration of copper vacancies (VCu), 2004 to 12.6% in 2014,2 they still lie far below those of which is a beneficial shallow acceptor.15,16

Downloaded via LIB4RI on November 26, 2019 at 07:21:09 (UTC). competing technologies like Cu(In,Ga)Se2 and CdTe that have It has been shown that CZTSSe absorbers and related 3 fi − surpassed 22%. One of the major issues is the signi cant Voc sulfur selenium alloys crystallize in the kesterite-type structure fi fi de cit in these devices de ned relative to the bandgap Eg of the where the band gap varies from 1.0 eV for pure selenide − absorber or relative to the Voc in the Shockley Queisser limit (CZTSe) to 1.5 eV for pure sulfurized (CZTS), opening the 4 − for the same band gap (Voc,SQ(Eg)). Kesterite devices show a possibility to tailor the band gap of kesterite through the S Se See https://pubs.acs.org/sharingguidelines for options on how to legitimately share published articles. fi − de cit (Eg/q Voc) larger than 0.55 V whereas competing content. Additionally, the structural instability due to the low technologies have reduced these losses to less than 0.4 V.5 In enthalpy cost of swapping Cu and Zn atoms in kesterites has fi ff 17 the literature, the lowest values of Voc de cit in devices have also been shown to a ect the band gap. In fact, the ordered been obtained by means of interfacial and compositional CZTSe (Cu2ZnSnSe4) has a band gap 100 meV higher than 6,7 18 ́ optimization with the highest achieved Voc relative to the the disordered one. Marquez et al. observed that Cu-poor band gap of a kesterite solar cell being still 0.4 V lower than CZTSe had a higher band gap and Voc, linked to an increased 8 V . ordering of the Cu/Zn sublattice, while the Voc,def remained oc,SQ 19 Several mechanisms have been investigated as the origin for constant. Similarly, through annealing procedures with − the large voltage losses in CZTSSe solar cells.9 11 A primary increasing temperatures and subsequent rapid cool-down, a − mechanism is thought to be related to the high defect density reversible order disorder transition was shown to occur at a 12,13 ° and associated band tailing of CZTSSe materials, which critical temperature of about 200 C, leading to a band gap shift equivalent to the one observed with the change in Cu are attributed to the multielement composition nature of the 20 quaternary CZTSSe phase. The similar ionic radii, and content. comparable valences of elements like copper and zinc, lead to a narrow chemical stability region and multiple defects with Received: February 21, 2019 low activation energies.14 The best performing devices have an Accepted: May 9, 2019 off-stoichiometric absorber composition, more specifically Cu- Published: May 9, 2019

The strong dependence of the band gap of kesterite kT JVph,SQ ()oc absorbers on their composition and processing condition, V =+B ln 1 oc,SQ q J coupled with the complexity of quantifying the band gap 0,SQ (2) 21 energy of a disordered system such as CZTSSe, raises the i y question of whether a V loss analysis solely related to the where Jph,SQ is the photocurrentj densityz in the radiative limit oc and J is the SQ darkj saturation currentz density. In practice, band gap energy gives relevant information concerning the 0,SQ j z origin of the losses and their dependence on material Jph,SQ(Voc) can bek replaced by the{ measured short-circuit current density (J ) at the corresponding light intensity. As properties. From the reciprocity principle and the measured sc discussed in ref 23, this assumption introduces a small error in external quantum efficiency, Rau et al.22 introduced a radiative the calculation of the open circuit voltages of some millivolts limit for the open circuit voltage that incorporates the actual that can be neglected. The J is obtained directly from the absorption tail of the materials, as expressed via the external 0,SQ ffi band gap Eg following the detailed balance of absorption and quantum e ciency (EQE) spectrum. On the basis of this work, emission in solar cell as expressed by Shockley and Queisser:4 Yao et al. introduced another way to quantify the losses in solar 23 ff ∞ cells, where they di erentiated the losses due to an extended Jq= ϕ ()d EE Δ 0,SQ ∫ BB absorption onset ( Voc,abs) from the losses due to nonradiative Eg (3) recombination (ΔV ), that are dependent on the ratio of oc,nrad where a step function for the external quantum efficiency at the radiative to nonradiative recombination rates. This approach ϕ band gap is assumed. BB is the spectral blackbody emission was used on organic solar cells to distinguish nonradiative fl losses from the total losses to indicate how changes in material ux density in the forward direction integrated from the 24,25 surface of the blackbody at the cell temperature Tc or processing could bring Voc closer to the radiative limit. In this work we focus on a series of CZTSSe solar cells E2 1 where compositional variation, namely, the Sn content, was ϕπBB(,)ET =× 2 32 ff hc E shown to a ect Voc, as well as the band gap energy of the exp− 1 ()()kTBc (4) absorber in a similar manner to the ordering effect of the Cu/ fi −2 −1 −1 ’ Zn sublattice. We rst show how a method relying solely on Eg which is expressed in units of cm s eV . Here h is Planck s fi to quantify the Voc de cit depends strongly on the way Eg is constant and c is the speed of light in vacuum (we consider the calculated. We then use the method described above refractive index of the external medium surrounding the cell to 23 26 developed by Yao et al. to calculate the radiative limit of be ns = 1). Using a similar approach, but considering the ffi the voltage (Voc,rad). This approach has never been applied to actual quantum e ciency of the cell (EQE(E)), we can express CZTSSe absorbers, but it proves to be very relevant, since the the radiative dark saturation current J0,rad as the integral of the bandgap cannot be reliably determined by traditional methods, EL emission from the cell 21 fi due to material complexity. Surprisingly, we nd that this Voc Jq==ϕϕ()d EEqEE EQE() ()dE increase with Sn content was accompanied by an increase 0,rad ∫∫EL BB (5) Δ ff rather than a decrease of Voc,nrad, indicating a negative e ect ϕ fl where EL is the spectral photon ux density emitted by the of the Sn content on the nonradiative relative to radiative ’ ϕ cell. We used Rau s reciprocity principle to write EL as recombination rate. By measuring both temperature dependent ϕ 22 EQE BB for the cell at equilibrium. Away from equilibrium, current voltage characteristic (JV-T) and temperature depend- δϕ ent capacitance-frequency (Cf−T), we discard the hypothesis the excess electroluminescence emission ( em(E)) is related to the internal voltage V experienced by the cell that this improvement is due to a change in the defect int distribution in the absorber structure and show that it can be qVint related to the interfacial quality between the absorber and the δϕϕem(EEET )=− EQE( ) BB ( , ) exp 1 buffer layers. The type of analysis presented here is applied to kTB (6) further characterize the different recombination mechanisms ÅÄ ÑÉ δϕ Thus, we can calculate EQE(EÅ) byi measuringy Ñ em(E)at that limit the V of CZTSSe and other devices and identify ff Å j z Ñ oc di erent injection currents andÅ by usingj thez knownÑ form of optimization routes to increase V . ϕ Å j z Ñ oc BB(E,T). Since electroluminescenceÇÅ k can{ beÖÑ measured at Voltage Loss Calculation Method. For solar cells, Voc is deeper photon energies in the tail of absorption than fi fl de ned by the balance between the absorbed photon ux and photocurrent, we can use the relation between δϕ (E) and fl em the recombination ux. In other words, the recombination EQE(E) to extend the quantum efficiency spectrum to lower current density Jrec and the photocurrent density Jph are equal energy by several tenths of an electronvolt beyond the range at open circuit, Jrec(Voc)=Jph(Voc). Using the nonideal diode that is accessible through direct electrical measurement. In equation we can typically express Voc as practice, it is difficult to quantify the internal voltage of the cell at fixed injection current. Therefore, the EQE(E) spectrum nkT JVph()oc extracted from EL at any applied bias is scaled by a constant V =+id B ln 1 oc q J factor in order to coincide with edge of the measured quantum 0 (1) efficiency spectrum using a calibrated electrical setup. Using the extended quantum efficiency, measured in this way, we can ji zy where nid is the idealityj factor, kBzis the Boltzmann constant, q calculate the achievable voltage if only radiative recombination j z is the elementary charge,j and J0 isz the dark saturation current occurs, density (neglectingk any effect of{ shunt resistance at open circuit). Both J0 and nid depend on the dominant kT J − V =+B lnsc 1 recombination process. The Shockley Queisser (SQ) limit oc,rad q J for the open-circuit voltage is similarly given by 0,rad (7) i y 2830 j z DOI: 10.1021/acs.jpclett.9b00506 j z J. Phys. Chem. Lett. 2019, 10, 2829−2835 j z k { The Journal of Physical Chemistry Letters Letter

Figure 1. (a) Normalized EL spectra for the four different cells. All EL spectra were acquired using an injection current density of 40 mA cm−2. (b) Measured EQE for the four cells (bold lines) and the extended EQE reconstructed one from their EL spectra (short dashed lines). The full PL spectra are presented in the Supporting Information, Figure S10. where we use the fact that nid = 1 for radiative recombination (Table S1). The Cu/Sn ratio decreased with increasing Sn and let J0 = J0,rad in the radiative limit. We can now express the content as expected, while the ratios Cu/(Zn + Sn) and Zn/Sn excess voltage losses due to the dominating nonradiative losses are in the Cu-poor and Zn-rich regions compared to 22,23 15,16 ff as stoichiometric Cu2ZnSn(S,Se)4. X-ray di raction measurements (Figure S1b) confirm decreasing disorder of the Cu/Zn kT J Δ=−=−B 0,rad sublattice with Sn increasing content, through the shift of the VVVoc,nrad oc,rad oc ln θ q J0 008 peak toward higher 2 values (further details are presented in the Supporting Information). However, such a shift could kT B i y also be caused by an overlap of different kinetics due to change =− ln(QE (Voc )) j z q LED j z j z (8) in composition. Therefore, additional experiments would be k { required to verify this interpretation. where QELED(Voc) is the electroluminescence quantum ffi Current density−voltage (JV) characteristics under AM1.5G e ciency of the solar cell at an applied bias of Voc. The latter expression emphasizes the link between the efficiency of a solar simulated solar irradiation show an increase in Voc with Sn cell and that of a light emitting diode. Excess nonradiative content until 31.2 at. % (device C) and a subsequent drop for voltage losses are detrimental for the efficiency of solar cells. device D (Table 2 and Figure S2). The poor performance of In the case where one can accurately measure the band gap device D appears to be caused by the formation of a Sn(S,Se)x of the absorber, we can additionally quantify the excess losses secondary phase, as shown with XRD measurements (Figure due to a nonsharp absorption onset by calculating the SQ limit S1a), whereas this phase is not detected for the rest of the 4 series. Overall, the PCEs of these devices follow a trend for the Voc (Voc,SQ). The abrupt absorption edge considered in the SQ theory does not apply in the presence of sub band gap comparable to that of Voc (Figure S2) with the highest efficiency achieved for device C with a PCE of 8.3%. absorption that is clearly observed in CZTSSe devices. This 28 difference allows the excess absorption open circuit voltage loss Larramona et al. also observed the existence of an optimal to be defined as Sn concentration for device performance, above which increasing Sn content causes a reduction in efficiency due to ΔVVoc,abs=− oc,SQ V oc,rad (9) the formation of secondary phases. However, for CZTSSe devices where strong band tailing Emission and Absorption Properties. In order to understand complicates the calculation of the band gap, this equation of the origin of the higher Voc in device C compared to the other Δ devices, we proceeded to measure EL, photoluminescence Voc,abs will be subject to uncertainty. Nonetheless, the use of V to quantify the excess nonradiative losses gives reliable (PL), and sub-bandgap EQE spectra for all devices. Figure 1a oc,rad presents their EL spectra, which originate from photons information on the nonradiative voltage losses even when Eg is uncertain. emitted during recombination of the injected or photoexcited Synthesis of Absorbers and Device Performance. Photovoltaic charge carriers, respectively. We note that the slight red-shifted devices of structure glass/Mo/CZTSSe/CdS/i-ZnO/Al:ZnO/ emission of the EL emission compared to the PL emission can − ff 29 MgF are prepared using CZTSSe absorbers in which the Sn be attributed to the Moss Burstein e ect (Figure S10 for the 2 fi content, measured as nominal atomic percentage (at. %), is PL). Signi cantly, when increasing the Sn content from 27.6 to controlled by varying the SnCl2 concentration in the precursor 32.9 at. % a blue shift in both the EL and PL peaks is observed. solution as presented elsewhere.27 Devices A, B, C, and D The strong blue shift in the luminescence upon increasing Sn correspond to CZTSSe absorbers with nominal Sn concen- content suggests either an increase in the band gap of the trations of 27.6, 29.5, 31.2, and 32.9 at. %, respectively. For material, probably related to a reduction in disorder of the 18 lower concentrations the formation of the Cux(S,Se) phase is kesterite crystal, or a change in properties of emissive defects observed, while the highest Sn content is the limit at which close to the band edges. For example, a blue shift in Sn(S,Se)x phases started to form. These secondary phases luminescence could, in principle, result from an increase in cause performance degradation and shunting of the solar cells. the density of shallow defects near the band edge, such as the The chemical compositions of the absorber layers were VCu +ZnCu defects, relative to the density of deep defects, or a fl 30,31 determined by X-ray uorescence (XRF) measurements decrease in the density of the ZnCu +CuZn defect. A similar

2831 DOI: 10.1021/acs.jpclett.9b00506 J. Phys. Chem. Lett. 2019, 10, 2829−2835 The Journal of Physical Chemistry Letters Letter blue shift of the band gap upon changing Sn content has been limit of these devices with increasing Sn content. Using the two observed in such cells when decreasing the Cu content.32 bandgap extracted previously (Table 1), we hence calculated Figure 1b shows the measured EQE as well as the sub- Voc,SQ for the four devices and compared it to the calculated bandgap EQE spectra reconstructed from the EL measure- Voc,rad values (Table 2). From Table S3, it is clear that neither ments using eq 6. The excellent overlap of the measured EQE method of calculating the band gap can accurately replicate the fi curve and the reconstructed EQE curve justi es the use of the trend in Voc,rad. method to extend the measured EQE using the luminescence We proceed to calculate the contribution of nonradiative 33 Δ measurement. Importantly, the same blue shift that we voltage loss ( Voc,nrad) for the above device series using eq 8 ff observed in the EL and PL with Sn content is observed in the and Voc,rad (from Table 2) and hence QELED for the di erent sub-band gap EQE. Notably, the slope of the tail of the devices in the series. From Table 2, we note that Voc,rad reconstructed EQE below the EL peak does not change increases by more than 100 mV across the series, whereas fi signi cantly with increasing Sn content. If we consider a model Voc increases by only 60 mV, from 423 to 485 mV. This leads 34 Δ of tail states below those band gap energies, this suggests that to a Voc,nrad that is higher by more than 60 mV in device D the distribution of these tail states does not change with Sn compared to device A, and consequently a lower QELED (Table content. 2). In other words, a larger fraction of charge carriers Comparison of Voltage Losses Analysis. First, we estimate the recombine radiatively rather than nonradiatively in device A voltage deficit in these cells by comparing the bandgap with the as compared to device D. From these results we can say that measured open circuit voltage, as is common in the literature.32 the CZTSe absorber with the lowest Sn content (device A) has We estimate the band gap of the cells using two different a V that is the closest to its radiative limit among this series. fi fl oc methods, rst from the in ection point of the EQE curve when Moreover, device A shows the highest QELED of the series with 13 −5 plotted on a linear axes (Figure S4) (Eg,EQE), and second by a value around 5 × 10 %, which is among the highest fitting the EL spectrum (Figure S5,Table S2) using the method reported values for CZTSe devices36,37 but remains several 35 developed by Katahara et al. (Eg,EL). The band gaps extracted orders of magnitude lower than typical values for CIGS or using these methods differ significantly, as shown in Table 1, silicon solar cells which are 0.03% and 0.13%, respectively.38 fi The signi cantly lower QELED of our investigated CZTSe Table 1. Summary of the Band Gap Loss Analysis for the devices compared to CIGS or silicon suggests enhanced Four Different Devices nonradiative recombination. Hence, to further investigate what − controls QELED for CZTS devices, we proceeded to use Cf T Sn content Eg,EQE Eg,EL Voc Voc,def,EQE Voc,def,EL label (at. %) (eV) (eV) (mV) (mV) (mV) and JV-T to understand the trend observed with changing Sn A 27.6 1.13 1.04 423 707 617 content. Factors Affecting QELED. Measuring the temperature depend- B 29.5 1.14 1.07 453 687 617 ff C 31.2 1.14 1.11 485 655 625 ence of the capacitance of the devices at di erent frequencies is D 32.9 1.15 1.12 465 685 655 a commonly used method in the literature to characterize defects in chalcogenide materials or the properties of the − ff interfaces with other layers.39 41 In this work we have and result in very di erent trends in the voltage losses; if we − rely on E from the EQE spectrum, the V deficit reaches a measured Cf T for the four devices in the series, at g oc temperatures ranging from 123 to 323 K. Figure 2a shows minimum for device C, whereas for Eg values derived from EL − the losses are similar for the first three devices and increase the Cf T curves for device A, while the curves for the other ffi devices are presented in the Supporting Information (Figure only for device D (Table 1). This emphasizes the di culty of fl S5). The in ection point frequency (f t) was subsequently relying on the band gap to understand the trends in voltage ff losses with material composition in a disordered material such extracted from the C-f curves for di erent temperatures for all the devices of the series. In previous work f t is assumed to as CZTSSe. ffi In order to obtain more reliable values for the voltage losses, relate to the emission coe cient of the defect state and ff therefore to its energy.41,42 Thus, we were able to extract the we calculate Voc,rad of the di erent cells from the extended EQE − spectrum. Table 2 shows the calculated values, showing that activation energy of the dominant trap state in a Shockley − Read Hall representation (Ea,CfT) from the slope of an Arrhenius plot of f t (Figure 2b). As kesterite absorbers are Table 2. Summary of the Voltage Loss Analysis for the Four ff Cells with Different Sn Content p-type, Ea,CfT is considered to be the energy di erence between the trap energy (Et) and the valence band maximum energy Δ − Sn content (at. Voc,rad Voc Voc,nrad (Ev), which can therefore be written as Ea,CfT = Et Ev. Figure label %) (mV) (mV) (mV) QELED (%) 3a shows E calculated using this procedure for all the − a,CfT A 27.6 799 423 376 5.2 × 10 5 devices, together with the band gap extracted from the EL − B 29.5 840 453 387 3.3 × 10 5 spectra. Clearly, the relative energy of the dominant trap state − C 31.2 888 485 403 1.8 × 10 5 around 0.1 eV does not change significantly with Sn content. − D 32.9 904 465 439 4.6 × 10 6 Similar behavior is observed by Larramona et al.28 where the activation energy of a shallow defect with energy between 120 Voc,rad increases with increasing Sn content, where the device and 170 meV is not correlated with Sn content. Further, fi with the highest Sn content (device D) has a Voc,rad that is 100 apparent carrier concentration pro les were extracted from meV higher than the device with the lowest Sn content (device capacitance−voltage (CV) measurements at room temperature A). The trend in Voc,rad is a quantitative reproduction of the for devices A, C and D (Figure S7, device B data are observed (qualitative) blue shift in the EQE onset as well as unavailable) with a voltage sweep from −1 to +0.5 V. The the EL and PL peak seen in Figure 1 and can be understood as profiles are comparable for all the devices, showing a doping 16 −3 an increase in the maximum achievable Voc in the radiative concentration on the order of 10 cm at 0 V. The measured

2832 DOI: 10.1021/acs.jpclett.9b00506 J. Phys. Chem. Lett. 2019, 10, 2829−2835 The Journal of Physical Chemistry Letters Letter

Figure 2. (a) Representative temperature-dependent capacitance−density frequency measurements in the temperature range from 123 to 323 K with 10 K steps and frequencies from 100 Hz to 1 MHz of device A (Sn content of 27.6 at. %). (b) Arrhenius plot of the inﬂection frequencies for device A.

Figure 3. (a) Comparison among band gap energy (Eg,EL) as obtained from EL measurements, activation energy of the main recombination mechanism (Ea,JVT) obtained by JVT measurements, and activation energy of the main defect (Ea,CfT) obtained by admittance spectroscopy for increasing Sn content. (The measurement error is too small to be properly visualized by the error bars.) (b) Temperature-dependent JV fi measurement (dark curve: dotted line, light curve: solid line) of device A (Sn content of 27.6 at. %). The inset shows a linear tofVoc extrapolated to T = 0 K; a fitting error of 1% is taken into account. trap state is therefore believed to be related to the defect reasons for this are either worsened interface quality, due to chemistry in the near-surface region or a transport barrier as the presence of domains of antibonding boundaries45,46 reported by Werner et al.43 Deep defects were not detected shunting paths on the nanoscale,47 or worsened band with the configuration for capacitance measurements presented alignment, specifically with the CdS buffer layer as Sn is here. expected to mainly affect the conduction band minimum of the Note that defect densities and energies are usually expected absorber. The latter is supported by first-principles studies ff to strongly a ect QELED of the device; however, in the studied showing that the conduction band minimum is dominated by fi series QELED changed signi cantly with Sn content, while the antibonding Sn s and Se p hybrid orbitals while the valence trap states properties remained unchanged. This observation band minimum does not involve Sn orbitals; thus a variation in fl suggests that the measured change in QELED with Sn content Sn content will predominantly in uence the conduction results not from trap states in the absorber inferred from Cf−T band.48,49 Device A shows the smallest difference between ff in these devices, but from a di erent cause. Eg,EL and Ea,JVT values, which amounts to about 0.05 eV. This Finally, in order to investigate this further, we carried out means that the main recombination mechanism has an energy temperature-dependent JV measurements for device A under closer to the band gap of the absorber, thus a better band AM1.5G illumination (Figure 3b), with similar plots for the alignment with the buffer layer, than the devices of higher Sn − rest of the series shown in Supporting Information Figure S6. content.50 52 An increasing mismatch of the absorber layer The crossover of illuminated and dark JV-T curves becomes and buffer layer conduction bands could explain the decreased more pronounced at lower temperatures, whereas the QELED with Sn content through increasing nonradiative losses increasing rollover leads to a complete blocking of the current via surface recombination at the interface with the buffer layer. at the lowest temperature of 123 K. The inset shows the The present study highlights that quantifying the Voc loss as ff temperature dependence of the Voc,wherethelinear the di erence between the measured device Voc and the band extrapolation to 0 K provides the activation energy of the gap of the absorber is not the best metric for determining the 44 dominant recombination mechanism Ea,JVT. For device A the voltage losses in compositionally complex absorbers like ff obtained Ea,JVT = 0.99 eV is close to the derived bandgap Eg,EL kesterites. By using two di erent methods to determine the = 1.04 eV; thus the dominant recombination is within the bulk bandgap, using either the absorption or emission spectra of the of the absorber rather than at the interface. While the band gap devices, we showed that the different methods lead to very ff fi increases with Sn content, Ea,JVT decreases slightly. Possible di erent values in the Voc de cit relative to the bandgap, and

2833 DOI: 10.1021/acs.jpclett.9b00506 J. Phys. Chem. Lett. 2019, 10, 2829−2835 The Journal of Physical Chemistry Letters Letter ff quantitatively di erent Voc loss trend in a series of solar cells STARCELL (H2020-NMBP-03-2016-720907). The authors with varying Sn content. Further, we show that by instead thank Flurin Eisner and Xingyuan Shi for their help with the using the radiative limit to the open circuit voltage (Voc,rad) measurement and their feedbacks. calculated from electroluminescence (EL) and external ffi quantum e ciency (EQE) measurements, we can more ■ REFERENCES reliably compare the voltage losses for the different devices (1) Siebentritt, S.; Schorr, S. Kesterites-a Challenging Material for in the series and subsequently quantify the electrolumines- − cence quantum efficiency (QE ) of the different devices. Solar Cells. Prog. Photovoltaics 2012, 20 (5), 512 519. LED (2) Wang, W.; Winkler, M. T.; Gunawan, O.; Gokmen, T.; Todorov, Interestingly, for this series of cells, the Voc increases with T. K.; Zhu, Y.; Mitzi, D. B. Device Characteristics of CZTSSe Thin- increasing Sn content from 423 mV to 465 mV, while the Film Solar Cells with 12.6% Efficiency. Adv. Energy Mater. 2014, 4 × −5 × −6 QELED decreases from 5 10 %to5 10 %. This result (7), 1301465. shows that while increasing Sn content increases device Voc,it (3) Green, M. A.; Hishikawa, Y.; Dunlop, E. D.; Levi, D. H.; Hohl- actually degrades the radiative efficiency of the device, Ebinger, J.; Ho-Baillie, A. W. Y. Solar Cell Efficiency Tables (Version increasing the loss in Voc due to nonradiative recombination. 52). Prog. Photovoltaics 2018, 26 (7), 427−436. ff Regarding the origin of this e ect, the decrease in QELED (4) Shockley, W.; Queisser, H. Detailed Balance Limit of Efficiency appears not to be related to the defect properties of the of P-n Junction Solar Cells. J. Appl. Phys. 1961, 32, 510−519. absorber as no significant change in defect energy activation (5) Rey, G.; Redinger, A.; Sendler, J.; Weiss, T. P.; Thevenin, M.; Guennou, M.; El Adib, B.; Siebentritt, S. The band gap of was observed. In fact, the solar cell with the best QELED shows the best interface quality of the series as inferred from the JV-T Cu2ZnSnSe4: Effect of order-disorder. Appl. Phys. Lett. 2014, 105, measurement. Further investigations are needed to fully 112106. (6) Redinger, A.; Unold, T. (SI) High Surface Recombination understand what controls QELED in kesterite solar cells and ffi Velocity Limits Quasi-Fermi Level Splitting in Kesterite Absorbers. how it is linked to the overall power conversion e ciency of Sci. Rep. 2018, 1874. the devices. We anticipate that this type of analysis will prove (7) Haass, S. G.; Andres, C.; Figi, R.; Schreiner, C.; Bürki, M.; useful in analyzing the impact of material composition, Romanyuk, Y. E.; Tiwari, A. N. (SI) Complex Interplay between processing, and device architecture on the voltage losses in Absorber Composition and Alkali Doping in High-Efficiency Kesterite other varieties of thin-film solar cells. Solar Cells. Adv. Energy Mater. 2018, 8, 1701760. (8) Redinger, A.; Siebentritt, S. Loss Mechanisms in Kesterite Solar ■ ASSOCIATED CONTENT Cells. In Copper Zinc Tin Sulfide-Based Thin-Film Solar Cells; John − *S Supporting Information Wiley & Sons Ltd., 2014; pp 363 386. The Supporting Information is available free of charge on the (9) Repins, I. L.; Li, J. V.; Kanevce, A.; Perkins, C. L.; Steirer, K. X.; ACS Publications website at DOI: 10.1021/acs.jp- Pankow, J.; Teeter, G.; Kuciauskas, D.; Beall, C.; Dehart, C.; et al. Effects of Deposition Termination on Cu2ZnSnSe4device Character- clett.9b00506. istics. Thin Solid Films 2015, 582, 184−187. Experimental section, XRF and XRD of the different (10) Mitzi, D. B.; Gunawan, O.; Todorov, T. K.; Wang, K.; Guha, S. absorbers, device perfomance data, EQE spectra, The Path towards a High-Performance Solution-Processed Kesterite electroluminecence spectra fitting procedure, comple- Solar Cell. Sol. Energy Mater. Sol. Cells 2011, 95 (6), 1421−1436. mentary voltage losses analysis, temperature dependent (11) Sperling, R. A.; Parak, W. J.; Ackerson, C. J.; Jadzinsky, P. D.; capacitance−frequency (Cf−T) plots for the remaining Kornberg, R. D.; Akerman, M. E.; Chan, W. C. W.; Laakkonen, P.; devices, temperature-dependent current density−voltage Bhatia, S. N.; Ruoslahti, E.; et al. Surface Modification, Functionaliza- tion and Bioconjugation of Colloidal Inorganic Nanoparticles. Philos. plots for the remaining devices, capacitance voltage − ff Trans. R. Soc., A 2010, 368 (1915), 1333 1383. measurements of di erent devices, and full PL spectra (12) Romero, M. J.; Du, H.; Teeter, G.; Yan, Y.; Al-Jassim, M. M. (PDF) Comparative Study of the Luminescence and Intrinsic Point Defects in the Kesterite Cu2ZnSnS4 and Chalcopyrite Cu(In,Ga)Se 2 Thin ■ AUTHOR INFORMATION Films Used in Photovoltaic Applications. Phys. Rev. B: Condens. Matter − Corresponding Author Mater. Phys. 2011, 84 (16), 1 5. * (13) Gokmen, T.; Gunawan, O.; Todorov, T. K.; Mitzi, D. B. Band E-mail: [email protected]. Tailing and Efficiency Limitation in Kesterite Solar Cells. Appl. Phys. ORCID Lett. 2013, 103 (10), 103506. Mohammed Azzouzi: 0000-0001-5190-9984 (14) Shin, D.; Saparov, B.; Mitzi, D. B. Defect Engineering in Author Contributions Multinary Earth-Abundant Chalcogenide Photovoltaic Materials. Adv. # Energy Mater. 2017, 7 (11), 1602366. These authors contributed equally (15) Chen, S.; Walsh, A.; Gong, X. G.; Wei, S. H. Classification of Notes Lattice Defects in the Kesterite Cu2ZnSnS 4 and Cu2ZnSnSe4 Earth- The authors declare no competing financial interest. Abundant Solar Cell Absorbers. Adv. Mater. 2013, 25 (11), 1522− 1539. ■ ACKNOWLEDGMENTS (16) Kumar, M.; Dubey, A.; Adhikari, N.; Venkatesan, S.; Qiao, Q. M.A. thanks the UK Engineering and Physical Sciences Strategic Review of Secondary Phases, Defects and Defect-Complexes in Kesterite CZTS−Se Solar Cells. Energy Environ. Sci. 2015, 8 (11), Research Council (ESPRC) for a postgraduate studentship. 3134−3159. J.N. acknowledges funding from the EPSRC (grant numbers (17) Bourdais, S.; Chone,́ C.; Delatouche, B.; Jacob, A.; Larramona, EP/P005543/1, EP/M025020/1), the EPSRC Supersolar Hub G.; Moisan, C.; Lafond, A.; Donatini, F.; Rey, G.; Siebentritt, S.; et al. (EP/P02484X/1), and the European Research Council under Is the Cu/Zn Disorder the Main Culprit for the Voltage Deficit in the European Union’s Horizon 2020 research and innovation Kesterite Solar Cells? Adv. Energy Mater. 2016, 6 (12), 1502276. program (grant agreement No 742708). A.C.-V. acknowledges (18) Rey, G.; Redinger, A.; Sendler, J.; Weiss, T. P.; Thevenin, M.; funding from Horizon2020 program under the project Guennou, M.; El Adib, B.; Siebentritt, S. The Band Gap of

2834 DOI: 10.1021/acs.jpclett.9b00506 J. Phys. Chem. Lett. 2019, 10, 2829−2835 The Journal of Physical Chemistry Letters Letter

Cu2ZnSnSe4: Effect of Order-Disorder. Appl. Phys. Lett. 2014, 105, (36) Yamaguchi, M.; Yamada, H.; Katsumata, Y.; Lee, K. H.; Araki, 112106. K.; Kojima, N. Efficiency Potential and Recent Activities of High- (19) Marquez,́ J.; Neuschitzer, M.; Dimitrievska, M.; Gunder, R.; Efficiency Solar Cells. J. Mater. Res. 2017, 32 (18), 3445−3457. Haass, S.; Werner, M.; Romanyuk, Y. E.; Schorr, S.; Pearsall, N. M.; (37) Green, M. A. Radiative Efficiency of State-of-the-art Photo- Forbes, I. Systematic Compositional Changes and Their Influence on voltaic Cells. Prog. Photovoltaics 2012, 20, 472−476. Lattice and Optoelectronic Properties of Cu 2 ZnSnSe 4 Kesterite (38) Kirchartz, T.; Rau, U.; Kurth, M.; Mattheis, J.; Werner, J. H. Solar Cells. Sol. Energy Mater. Sol. Cells 2016, 144, 579−585. Comparative Study of Electroluminescence from Cu(In,Ga)Se2and Si (20) Krammer, C.; Huber, C.; Zimmermann, C.; Lang, M.; Solar Cells. Thin Solid Films 2007, 515 (15 SPEC. ISS), 6238−6242. Schnabel, T.; Abzieher, T.; Ahlswede, E.; Kalt, H.; Hetterich, M. (39) Walter, T.; Herberholz, R.; Müller, C.; Schock, H. W. Reversible Order-Disorder Related Band Gap Changes in Cu2ZnSn- Determination of Defect Distributions from Admittance Measure- (S,Se)4 via Post-Annealing of Solar Cells Measured by Electro- ments and Application to Cu(In,Ga)Se2 Based Heterojunctions. J. reflectance. Appl. Phys. Lett. 2014, 105 (26), 262104. Appl. Phys. 1998, 80 (8), 4411. (21) Carron, R.; Andres, C.; Avancini, E.; Feurer, T.; Nishiwaki, S.; (40) Proskuryakov, Y. Y.; Durose, K.; Taele, B. M.; Oelting, S.  Pisoni, S.; Fu, F.; Lingg, M.; Romanyuk, Y. E.; Buecheler, S.; et al. Impedance Spectroscopy of Unetched CdTe/CdS Solar Cells Bandgap of Thin Film Solar Cell Absorbers: A Comparison of Various equivalent Circuit Analysis. J. Appl. Phys. 2007, 102 (2), 024504. Determination Methods. Thin Solid Films 2019, 669 (9), 482−486. (41) Gunawan, O.; Gokmen, T.; Warren, C. W.; Cohen, J. D.; (22) Rau, U.; Paetzold, U. W.; Kirchartz, T. Thermodynamics of Todorov, T. K.; Barkhouse, D. A. R.; Bag, S.; Tang, J.; Shin, B.; Mitzi, Light Management in Photovoltaic Devices. Phys. Rev. B: Condens. D. B. Electronic Properties of the Cu 2ZnSn(Se,S) 4 Absorber Layer Matter Mater. Phys. 2014, 90 (3), 1−16. in Solar Cells as Revealed by Admittance Spectroscopy and Related 2012 (23) Yao, J.; Kirchartz, T.; Vezie, M. S.; Faist, M. A.; Gong, W.; He, Methods. Appl. Phys. Lett. , 100 (25), 253905. (42) Weiss, T. P. Electrical Characterization of Kesterite Thin Film Z.; Wu, H.; Troughton, J.; Watson, T.; Bryant, D.; et al. Quantifying Absorbers and Solar Cells; University of Luxembourg, 2015. Losses in Open-Circuit Voltage in Solution-Processable Solar Cells. (43) Werner, F.; Siebentritt, S. Buffer Layers, Defects, and the Phys. Rev. Appl. 2015, 4 (1), 1−10. Capacitance Step in the Admittance Spectrum of a Thin-Film Solar (24) Tuladhar, S. M.; Azzouzi, M.; Delval, F.; Yao, J.; Guilbert, A. A. Cell. Phys. Rev. Appl. 2018, 9 (5), 54047. Y.; Kirchartz, T.; Montcada, N. F.; Dominguez, R.; Langa, F.; (44) Nadenau, V.; Rau, U.; Jasenek, A.; Schock, H. W.; Nadenau, V.; Palomares, E.; et al. Low Open-Circuit Voltage Loss in Solution- Rau, U.; Jasenek, A.; Schock, H. W. Electronic Properties of CuGaSe Processed Small-Molecule Organic Solar Cells. ACS Energy Lett. 2016, − 2 -Based Heterojunction Solar Cells. Part I. Transport Analysis. J. 1 (1), 302 308. Appl. Phys. 2000, 87, 584. (25) Qian, D.; Zheng, Z.; Yao, H.; Tress, W.; Hopper, T. R.; Chen, (45) Park, J.-S.; Kim, S.; Walsh, A. Opposing Effects of Stacking S.; Li, S.; Liu, J.; Chen, S.; Zhang, J.; et al. Design Rules for Faults and Antisite Domain Boundaries on the Conduction Band Minimizing Voltage Losses in High-Efficiency Organic Solar Cells. Edge in Kesterite Quaternary Semiconductors. Phys. Rev. Materials Nat. Mater. 2018, 17, 703. 2018, 2, 014602. (26) Nelson, J. The Physics of Solar Cells; published by Imperial (46) Kattan, N. A.; Griffiths, I. J.; Cherns, D.; Fermín, D. J. College Press and distributed by World Scientiﬁc Publishing Co., Observation of Antisite Domain Boundaries in Cu2ZnSnS4 by 2003 . Atomic-Resolution Transmission Electron Microscopy. Nanoscale (27) Ki, W.; Hillhouse, H. W. Earth-Abundant Element Photo- 2016, 8 (30), 14369−14373. voltaics Directly from Soluble Precursors with High Yield Using a (47) Tiwari, D.; Cattelan, M.; Harniman, R.; Saruna, A.; Abbas, A.; Non-Toxic Solvent. Adv. Energy Mater. 2011, 1 (5), 732−735. Bowers, J. W.; Fox, N. A.; Fermin, D. J. Mapping Shunting Paths at (28) Larramona, G.; Levcenko, S.; Bourdais, S.; Jacob, A.; Chone,́ the Surface of Cu2ZnSn(S,Se)4 Films via Energy-Filtered Photo- C.; Delatouche, B.; Moisan, C.; Just, J.; Unold, T.; Dennler, G. Fine- emission Microscopy. iScience 2018, 9,36−46. Tuning the Sn Content in CZTSSe Thin Films to Achieve 10.8% (48) Shu, Q.; Yang, J.-H.; Chen, S.; Huang, B.; Xiang, H.; Gong, X.- Solar Cell Efficiency from Spray-Deposited Water-Ethanol-Based G.; Wei, S.-H. Cu2Zn(Sn,Ge)Se4 and Cu2Zn(Sn,Si)Se4 Alloys as Colloidal Inks. Adv. Energy Mater. 2015, 5 (24), 1501404. Photovoltaic Materials: Structural and Electronic Properties. Phys. (29) Ashley, T.; Elliott, C. T.; Gordon, N. R.; Hall, R. S.; Maxey, C. Rev. B: Condens. Matter Mater. Phys. 2013, 87 (11), 115208. D.; Matthews, B. E. Room-Temperature Electroluminescence at (49) Chen, S.; Gong, X. G.; Walsh, A.; Wei, S.-H. Electronic Wavelengths of 5−7 Μm from HgCdTe Heterostructure Diodes. Structure and Stability of Quaternary Chalcogenide Semiconductors Appl. Phys. Lett. 1994, 65 (18), 2314−2316. Derived from Cation Cross-Substitution of II-VI and I-III-VI 2 (30) Yakushev, M. V.; Sulimov, M. A.; Marquez-Prieto,́ J.; Forbes, I.; Compounds. Phys. Rev. B: Condens. Matter Mater. Phys. 2009, 79, Krustok, J.; Edwards, P. R.; Zhivulko, V. D.; Borodavchenko, O. M.; 165211. Mudryi, A. V.; Martin, R. W. Influence of the Copper Content on the (50) Haight, R.; Barkhouse, A.; Gunawan, O.; Shin, B.; Copel, M.; Optical Properties of CZTSe Thin Films. Sol. Energy Mater. Sol. Cells Hopstaken, M.; Mitzi, B.; Haight, R.; Barkhouse, A.; Gunawan, O. − 2017, 168 (January), 69−77. Band Alignment at the Cu 2 ZnSn (SxSe1 x)4/CdS Interface. Appl. (31) Huang, D.; Persson, C. Band Gap Change Induced by Defect Phys. Lett. 2011, 98, 253502. Complexes in Cu2ZnSnS4. Thin Solid Films 2013, 535, 265−269. (51) Chen, S.; Walsh, A.; Yang, J.-H.; Gong, X. G.; Sun, L.; Yang, P.- (32) Haass, S. G.; Andres, C.; Figi, R.; Schreiner, C.; Bürki, M.; X.; Chu, J.-H.; Wei, S.-H. Compositional Dependence of Structural Romanyuk, Y. E.; Tiwari, A. N. Complex Interplay between Absorber and Electronic Properties of Cu 2 ZnSn(S,Se) 4 Alloys for Thin Film Composition and Alkali Doping in High-Efficiency Kesterite Solar Solar Cells. Phys. Rev. B: Condens. Matter Mater. Phys. 2011, 83 (12), Cells. Adv. Energy Mater. 2018, 8 (4), 1701760. 125201. (33) Müller, T. C. M.; Pieters, B. E.; Kirchartz, T.; Carius, R.; Rau, (52) Gao, S.; Jiang, Z.; Wu, L.; Ao, J.; Zeng, Y.; Sun, Y.; Zhang, Y. U. Effect of Localized States on the Reciprocity between Quantum Interfaces of High-Efficiency Kesterite Cu 2 ZnSnS(e) 4 Thin Film Efficiency and Electroluminescence in Cu(In,Ga)Se2 and Si Thin- Solar Cells. Chin. Phys. B 2018, 27 (1), 018803. Film Solar Cells. Sol. Energy Mater. Sol. Cells 2014, 129,95−103. (34) Hages, C. J.; Carter, N. J.; Agrawal, R. Generalized Quantum Efficiency Analysis for Non-Ideal Solar Cells: Case of Cu2ZnSnSe4. J. Appl. Phys. 2016, 119 (1), 014505. (35) Katahara, J. K.; Hillhouse, H. W. Quasi-Fermi Level Splitting and Sub-Bandgap Absorptivity from Semiconductor Photolumines- cence. J. Appl. Phys. 2014, 116 (17), 173504.

2835 DOI: 10.1021/acs.jpclett.9b00506 J. Phys. Chem. Lett. 2019, 10, 2829−2835